Dithienobenzofuran polymers and small molecules for electronic application

ABSTRACT

The present invention relates to polymers comprising a repeating unit of the formula (I), and compounds of formula (VIII), or (IX), wherein Y, Y 15 , Y 16  and Y 17  are independently of each other a group of formula (I), and their use as organic semiconductor in organic electronic devices, especially in organic photovoltaics and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers and compounds according to the invention can have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers and compounds according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes.

The present invention relates to polymers comprising a repeating unit ofthe formula (I) and compounds of formula (VIII), or (IX), wherein Y,Y¹⁵, Y¹⁶ and Y¹⁷ are independently of each other a group of formula (I),and their use as organic semiconductor in organic electronic devices,especially in organic photovoltaics (solar cells) and photodiodes, or ina device containing a diode and/or an organic field effect transistor.The polymers and compounds according to the invention can have excellentsolubility in organic solvents and excellent film-forming properties. Inaddition, high efficiency of energy conversion, excellent field-effectmobility, good on/off current ratios and/or excellent stability can beobserved, when the polymers and compounds according to the invention areused in organic field effect transistors, organic photovoltaics (solarcells) and photodiodes.

WO2010136401 relates to polycyclic dithiophenes of the following formula

wherein

R¹ and R¹′ independently of each other are H or a substituent, halogenor SiR⁶R⁴R⁵;

R² and R²′ may be the same or different and are selected fromC₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkynyl, C₄-C₂₅aryl,C₅-C₂₅alkylaryl or C₅-C₂₅aralkyl, each of which is unsubstituted orsubstituted, and if R³ and R³′ within the definition of X togethercomplete a ring structure, or X is a bridging group conforming to one ofthe formulae

R² and/or R²′ may also be halogen or hydrogen;

X is a divalent linking group selected from

Y and Y′ independently are selected from

n and p independently range from 0 to 6;

R³ and R³′ independently are hydrogen or a substituent, or are amino, ortogether, with the carbon atoms they are attached to, complete a 5- or6-membered unsubstituted or substituted hydrocarbon ring, or a5-membered unsubstituted or substituted heterocyclic ring comprising atleast one hetero atom selected from N, O, or S; as well as oligomers,polymers or copolymers comprising at least 2 structural units of theformula

The substances described in WO2010136401 are used in organic fieldeffect transistors, organic photovoltaics (solar cells) and photodiodes.

WO2011002927 relates to is directed to a (copolymer) compositioncomprising at least one donor acceptor copolymer, said at least onecopolymer comprising at least one first bithiophene repeat unit (donor)represented by formula

wherein R₁, R₂ and R′ are solubilizing groups or hydrogen. According toclaim 8 of WO2011002927 R¹ and R² may form a heterocyclic ring.

In addition, polymers comprising a bithiophene repeating unit aredescribed in EP2006291A1, US20110006287 and WO2011025454.

PCT/EP2013/056463 relates to organic electronic devices comprisingpolymers or small molecules comprising at least one (repeating) unit ofthe formulas (I) and (II)

Schroeder B. C. et al., Chem. Mater., 23 (2011) 4025-4031 describe theuse of polymers comprising monomers units of formula M1 and M2 in manicfield effect transistors:

James R. Durrant et al., J. Phys. Chem. Lett. 2012, 3, 140-144 report onthe contribution of photoinduced hole transfer to the devicephotocurrent for an OPV device with an active layer comprising a blendfilm of the small bandgap polymer

It is one object of the present invention to provide polymers, whichshow high efficiency of energy conversion, excellent field-effectmobility, good on/off current ratios and/or excellent stability, whenused in organic field effect transistors, organic photovoltaics (solarcells) and photodiodes.

Said object has been solved by polymers, comprising a repeating unit ofthe formula

wherein

R¹ and R² are independently of each other H, F, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E′ and/or interrupted by D′, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G′, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G′, or

R¹ and R² form together a group

wherein

R²⁰⁵, R²⁰⁶, R^(206′), R²⁰⁷, R²⁰⁸, R^(208′), R²⁰⁹ and R²¹⁰ areindependently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E′ and/or interrupted by D′, C₁-C₁₈alkoxy, orC₁-C₁₈alkoxy which is substituted by E′ and/or interrupted by D′,C₁-C₁₈fluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G′,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G′,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl which issubstituted by G′; CN, or —CO—R²⁸,

R⁶⁰¹ and R⁶⁰² are independently of each other H, halogen, C₁-C₂₅alkyl,C₃-C₁₂cycloalkyl, C₂-C₂₅alkenyl, C₂-C₂₅alkynyl, C₆-C₂₄aryl, C₆-C₂₄arylwhich is substituted by G′, C₇-C₂₅aralkyl, or C₇-C₂₅aralkyl which issubstituted by G′;

D′ is —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR⁶⁵—, —SiR⁷⁰R⁷¹—, —POR⁷²—,—CR⁶³═CR⁶⁴—, or —C≡C—, and

E′ is —OR⁶⁹, —SR⁶⁹, —NR⁶⁵R⁶⁶, —COR⁶⁸, —COOR⁶⁷, —CONR⁶⁵R⁶⁶, —CN, CF₃, orhalogen,

G′ is E′, C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by —O—,

R²⁸ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,

R⁶³ and R⁶⁴ are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl whichis substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—;

R⁶⁵ and R⁶⁶ are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl whichis substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—; or

R⁶⁵ and R⁶⁶ together form a five or six membered ring,

R⁶⁷ is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,

R⁶⁸ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,

R⁶⁹ is C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,

R⁷⁰ and R⁷¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl, orC₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, and

R⁷² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl.

Advantageously, the polymer of the present invention, or an organicsemiconductor material, layer or component, comprising the polymer ofthe present invention, can be used in organic light emitting diodes(PLEDs, OLEDs), organic photovoltaics (solar cells) and photodiodes, orin an organic field effect transistor (OFET).

The polymers of this invention preferably have a weight averagemolecular weight of 4,000 Daltons or greater, especially 4,000 to2,000,000 Daltons, more preferably 10,000 to 1,000,000 and mostpreferably 10,000 to 100,000 Daltons. Molecular weights are determinedaccording to high-temperature gel permeation chromatography (HT-GPC)using polystyrene standards. The polymers of this invention preferablyhave a polydispersity of 1.01 to 10, more preferably 1.1 to 3.0, mostpreferred 1.5 to 2.5. The polymers of the present invention arepreferably conjugated.

Oligomers of the present invention preferably have a weight averagemolecular weight below 4,000 Daltons.

In a preferred embodiment R¹ and R² form together a group

R²⁰⁵, R²⁰⁶, R²⁰⁷ and R²⁰⁸ are preferably H.

In another preferred embodiment R¹ and R² are a group of formula

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰² and R⁴⁰³ are independently of each other H, CN,F, CF³, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interruptedby —O—. R⁴⁰⁰, R⁴⁰¹, R⁴⁰² and R⁴⁰³ are preferably H.

R¹ and R² may be different, but are preferably the same.

In a preferred embodiment the present invention is directed to polymerscomprising a repeating unit of the formula

wherein R¹ and R² are independently of each other a group of formula

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are independently of eachother H, CN, F, CF₃, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—, or R¹ and R² form together a group

R⁶⁰¹ and R⁶⁰² may be the same or different and are selected fromC₁-C₂₅alkyl, or hydrogen; especially hydrogen. R¹ and R² are especiallya group of formula

very especially

Among the repeating units of formula I repeating units of formula

(Ia) are preferred.

The polymer may be a homopolymer of formula

wherein A is a repeating unit of formula (I), n is usually in the rangeof 4 to 1000, especially 4 to 200, very especially 5 to 150.

Alternatively, the polymer may be a polymer, comprising repeating unitsof the formula

especially

very especially a copolymer of formula

wherein

n is usually in the range of 4 to 1000, especially 4 to 200, veryespecially 5 to 150.

A is a repeating unit of formula (I), and

—COM¹- is a repeating unit

wherein

k is 0, 1, 2, or 3; l is 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1, 2,or 3;

Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are independently of each other a group of formulaand

such as, for example,

such as, for example,

wherein

X¹ is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′))—, —Ge(R¹¹)(R^(11′))—,—C(R⁷)(R^(7′))—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

such as, for example,

such as, for example,

wherein

X^(1′) is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—, —Ge(R¹¹⁷)(R^(117′))—,—C(R¹⁰⁶)(R¹⁰⁹)—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

R³ and R^(3′) are independently of each other hydrogen, halogen,halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, orC₁-C₂₅alkoxy;

R¹⁰⁴ and R^(104′) are independently of each other hydrogen, cyano,COOR¹⁰³, a C₁-C₂₅alkyl group, or C₆-C₂₄aryl or C₂-C₂₀heteroaryl,

R⁴, R^(4′), R⁵, R^(5′), R⁶, and R^(6′) are independently of each otherhydrogen, halogen, halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, whichmay optionally be interrupted by one or more oxygen or sulphur atoms;C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy;

R⁷, R^(7′), R⁹ and R^(9′) are independently of each other hydrogen,C₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen,or sulphur atoms; or C₇-C₂₅arylalkyl,

R⁸ and R^(8′) are independently of each other hydrogen, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; orC₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygenor sulphur atoms; or C₇-C₂₅arylalkyl,

R¹¹ and R^(11′) are independently of each other C₁-C₂₅alkyl group,C₇-C₂₅arylalkyl, or a phenyl group, which can be substituted one tothree times with C₁-C₈alkyl and/or C₁-C₈alkoxy;

R¹² and R^(12′) are independently of each other hydrogen, halogen,cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one, or moreoxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

wherein R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group; or

R¹⁰⁴ and R^(104′) are independently of each other hydrogen, C₁-C₁₈alkyl,C₆-C₁₀aryl, which may optionally be substituted by G, orC₂-C₈heteroaryl, which may optionally be substituted by G,

R¹⁰⁵, R¹⁰⁵′, R¹⁰⁶ and R^(106′) are independently of each other hydrogen,halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by oneor more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₁₈alkoxy,

R¹⁰⁷ is hydrogen, C₇-C₂₅arylalkyl, C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈perfluoroalkyl;C₁-C₂₅alkyl; which may be interrupted by —O—, or —S—; or —COOR¹⁰³;

R¹⁰⁸ and R¹⁰⁹ are independently of each other H, C₁-C₂₅alkyl,C₁-C₂₅alkyl which is substituted by E and/or interrupted by D,C₇-C₂₅arylalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or

R¹⁰⁸ and R¹⁰⁹ together form a group of formula ═CR¹¹⁰R¹¹¹, wherein

R¹¹⁰ and R¹¹¹ are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀heteroaryl,or C₂-C₂₀heteroaryl which is substituted by G, or

R¹⁰⁸ and R¹⁰⁹ together form a five or six membered ring, whichoptionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D, orC₇-C₂₅aralkyl,

D is —CO—, —COO—, —S—, —O—, or —NR^(112′)—,

E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR^(112′)R^(113′),—CONR^(112′)R^(113′), or halogen,

G is E, or C₁-C₁₈alkyl, and

R^(112′) and R^(113′) are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,

R¹¹⁵ and R^(115′) are independently of each other hydrogen, halogen,cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one, or moreoxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

wherein R¹¹⁶ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group;

R¹¹⁷ and R^(117′) are independently of each other C₁-C₂₅alkyl group,C₇-C₂₅arylalkyl, or a phenyl group, which can be substituted one tothree times with C₁-C₈alkyl and/or C₁-C₈alkoxy;

R¹¹⁸, R¹¹⁹, R¹²⁰ and R¹²¹ are independently of each other hydrogen,halogen, halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which mayoptionally be interrupted by one or more oxygen or sulphur atoms;C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy;

R¹²² and R^(122′) are independently of each other hydrogen, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; orC₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygenor sulphur atoms; or C₇-C₂₅arylalkyl.

R²⁰¹ is selected from hydrogen, a C₁-C₁₀₀alkyl group, —COOR¹⁰³, aC₁-C₁₀₀alkyl group substituted by one or more halogen atoms, hydroxylgroups, nitro groups, —CN, or C₆-C₁₈aryl groups and/or interrupted by—O—, —COO—, —OCO— or —S—; a C₇-C₂₅arylalkyl group, a carbamoyl group, aC₅-C₁₂cycloalkyl group, which can be substituted one to three times withC₁-C₁₀₀alkyl and/or C₁-C₁₀₀alkoxy, a C₆-C₂₄aryl group, in particularphenyl or 1- or 2 naphtyl which can be substituted one to three timeswith C₁-C₁₀₀alkyl, C₁-C₁₀₀thioalkoxy, and/or C₁-C₁₀₀alkoxy; andpentafluorophenyl;

R¹⁰³ and R¹¹⁴ are independently of each other C₁-C₂₅alkyl, which mayoptionally be interrupted by one, or more oxygen, or sulphur atoms,

R²⁰² and R²⁰³ may be the same or different and are selected from H, F,—CN, C₁-C₁₀₀alkyl, which may optionally be interrupted by one or moreoxygen, or sulphur atoms; and C₁-C₁₀₀alkoxy.

The above-mentioned repeating units COM¹ are known and can be preparedaccording to known procedures. With respect to DPP repeating units andtheir synthesis reference is, for example, made to U.S. Pat. No.6,451,459B1, WO05/049695, WO2008/000664, EP2034537A2, EP2075274A1,WO2010/049321, WO2010/049323, WO2010/108873, WO2010/115767,WO2010/136353, WO2010/136352 and PCT/EP2011/057878.

R³, R^(3′), R⁴ and R^(4′) are preferably hydrogen, or C₁-C₂₅alkyl.

R²⁰¹ is preferably a linear, or branched C₁-C₃₆alkyl group, such as, forexample, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl,isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl,1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl,1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl,especially n-dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,2-ethyl-hexyl, 2-butyl-hexyl, 2-butyl-octyl, 2-hexyldecyl,2-decyl-tetradecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl,or tetracosyl.

Advantageously, the groups R²⁰¹ can be represented by formula

wherein m1=n1+2 and m1+n1≦24. Chiral side chains can either behomochiral, or racemic, which can influence the morphology of thecompounds.

—COM¹- is preferably a repeating unit of formula

wherein R³, R^(3′), R⁴ and R^(4′) are independently of each otherhydrogen, or C₁-C₂₅alkyl;

R⁸ and R^(8′) are independently of each other hydrogen, or C₁-C₂₅alkyl;

R¹¹⁴ is a C₁-C₃₈alkyl group;

R²⁰¹ is a C₁-C₃₈alkyl group; and

R²⁰² and R^(203′) are independently of each other hydrogen orC₁-C₂₅alkyl.

In a particularly preferred embodiment COM¹ is selected from repeatingunits of formula (XVb), (XVb′), (XVe), (XVh), (XVh′), (XVu′), (XVu″),and (XVu′″), especially (XVb), (XVb′), (XVu′), (XVu″), and (XVu′″).

In a preferred embodiment of the present invention the polymer is acopolymer, comprising repeating units of formula

especially a copolymer of formula

wherein A and COM¹ are as defined above; n is a number which results ina molecular weight of 4,000 to 2,000,000 Daltons, more preferably 10,000to 1,000,000 and most preferably 10,000 to 100,000 Daltons. n is usuallyin the range of 4 to 1000, especially 4 to 200, very especially 5 to150. The polymer structure represented by formula III is an idealizedrepresentation of the polymer products obtained, for example, via theSuzuki polymerization procedure. The repeating unit of formula

can be incorporated into the polymer chain in two ways:

Both possibilities shall be covered by formula (III).

The polymers of the present invention can comprise more than 2 differentrepeating units, such as, for example, repeating units A, COM¹ and B,which are different from each other. In said embodiment the polymer is acopolymer, comprising repeating units of formula

wherein x=0.995 to 0.005, y=0.005 to 0.995, especially x=0.2 to 0.8,y=0.8 to 0.2, and x+y=1. B has the meaning of COM¹, with the provisothat B is different from COM¹. A and COM¹ are as defined above.

In another preferred embodiment of the present invention A is arepeating unit of formula (I), especially (Ia), as defined above, and

is a group of formula

wherein R³, R^(3′), R⁴ and R^(4′) are independently of each otherhydrogen or C₁-C₂₅alkyl;

R⁸ and R^(8′) are independently of each other hydrogen or C₁-C₂₅alkyl;and

R²⁰¹ is a C₁-C₃₈alkyl group.

COM¹ is preferably a repeating unit of formula (XVb′), (XVb′), (XVu′)and (XVu″).

Among the repeating units of formula (I) repeating units of formula (I)are preferred, wherein R¹ and R² are independently of each other a groupof formula

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are independently of eachother H, CN, F, CF₃, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—, or R¹ and R² form together a group

R¹ and R² are especially a group of formula

very especially a group of formula

R¹ and R² may be the different, but are preferably the same. R⁶⁰¹ andR⁶⁰² may be the different, but are preferably the same and are selectedfrom hydrogen, or C₁-C₂₅alkyl, especially hydrogen. Most preferred arerepeating units of formula (Ia).

Among the copolymers of formula III the following copolymers arepreferred:

wherein

n is 4 to 1000, especially 4 to 200, very especially 5 to 150;

R³, R^(3′), R⁴ and R⁴′ are independently of each other hydrogen orC₁-C₂₅alkyl;

R²⁰¹ is a C₁-C₃₈alkyl group, and

R⁶⁰¹ and R⁶⁰² are independently of each other hydrogen, or C₁-C₂₅alkyl;especially hydrogen. Polymers of formula (Ia1), (Ia2), (Ia6) and (Ia7)are more preferred.

Examples of particularly preferred polymers are shown below:

Copolymers of formula III can be obtained, for example, by the Suzukireaction. The condensation reaction of an aromatic boronate and ahalogenide, especially a bromide, commonly referred to as the “Suzukireaction”, is tolerant of the presence of a variety of organicfunctional groups as reported by N. Miyaura and A. Suzuki in ChemicalReviews, Vol. 95, pp. 457-2483 (1995). Preferred catalysts are2-dicyclohexylphosphino-2′,6′-di-alkoxybiphenyl/palladium(II)acetates,tri-alykl-phosphonium salts/palladium (0) derivatives andtri-alkylphosphine/palladium (0) derivatives. Especially preferredcatalysts are 2-dicyclohexylphosphino-2′,6′-di-methoxybiphenyl(sPhos)/palladium(II)acetate and, tri-tert-butylphosphoniumtetrafluoroborate ((t-Bu)₃P*HBF₄)/tris(dibenzylideneacetone) dipalladium(0) (Pd₂(dba)₃) and tri-tert-butylphosphine(t-Bu)₃P/tris(dibenzylideneacetone) dipalladium (0) (Pd₂(dba)₃). Thisreaction can be applied to preparing high molecular weight polymers andcopolymers.

To prepare polymers corresponding to formula III a dihalogenide offormula X¹⁰-A-X¹⁰ is reacted with an (equimolar) amount of a diboronicacid or diboronate corresponding to formula

or a dihalogenide of formula

is reacted with an (equimolar) amount of a diboronic acid or diboronatecorresponding to formula X¹¹-A-X¹¹, wherein X¹⁰ is halogen, especiallyBr, and X¹¹ is independently in each occurrence —B(OH)₂, —B(OY¹)₂,

wherein Y¹ is independently in each occurrence a C₁-C₁₀alkyl group andY² is independently in each occurrence a C₂-C₁₀alkylene group, such as—CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹C¹²—, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷,Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or aC₁-C₁₀alkyl group, especially —C(CH₃)₂C(CH₃)₂—, —CH₂C(CH₃)₂CH₂—, or—C(CH₃)₂CH₂C(CH₃)₂—, and Y¹³ and Y¹⁴ are independently of each otherhydrogen, or a C₁-C₁₀alkyl group, under the catalytic action of Pd andtriphenylphosphine. The reaction is typically conducted at about 0° C.to 180° C. in an aromatic hydrocarbon solvent such as toluene, xylene.Other solvents such as dimethylformamide, dioxane, dimethoxyethan andtetrahydrofuran can also be used alone, or in mixtures with an aromatichydrocarbon. An aqueous base, preferably sodium carbonate orbicarbonate, potassium phosphate, potassium carbonate or bicarbonate isused as activation agent for the boronic acid, boronate and as the HBrscavenger. A polymerization reaction may take 0.2 to 100 hours. Organicbases, such as, for example, tetraalkylammonium hydroxide, and phasetransfer catalysts, such as, for example TBAB, can promote the activityof the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int.Ed. Eng. 42 (2003) 1407 and references cited therein). Other variationsof reaction conditions are given by T. I. Wallow and B. M. Novak in J.Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G.Wegner in Macromol. Rapid Commun. 17 (1996) 239-252. Control ofmolecular weight is possible by using either an excess of dibromide,diboronic acid, or diboronate, or a chain terminator.

According to the process described in WO2010/136352 the polymerisationis carried out in presence of

a) a catalyst/ligand system comprising a palladium catalyst and anorganic phosphine or phosphonium compound,

b) a base,

c) a solvent or a mixture of solvents, characterized in that

the organic phosphine is a trisubstituted phosphine of formula

or phosphonium salt thereof, wherein X″ independently of Y″ represents anitrogen atom or a C—R^(2″) group and Y″ independently of X″ representsa nitrogen atom or a C—R^(9″) group, R^(1″) for each of the two R^(1″)groups independently of the other represents a radical selected from thegroup C₁-C₂₄-alkyl, C₃-C₂₀-cycloalkyl, which includes especially bothmonocyclic and also bi-and tri-cyclic cycloalkyl radicals, C₅-C₁₄-aryl,which includes especially the phenyl, naphthyl, fluorenyl radical,C₂-C₁₃-heteroaryl, wherein the number of hetero atoms, selected from thegroup N, O, S, may be from 1 to 2, wherein the two radicals R^(1″) mayalso be linked to one another,

and wherein the above-mentioned radicals R¹″ may themselves each bemono-or poly-substituted independently of one another by substituentsselected from the group hydrogen, C₁-C₂₀-alkyl, C₂-C_(2o)-alkenyl,C₃-C₈-cycloalkyl, C₂-C₉-hetero-alkyl, C₅-C₁₀-aryl, C₂-C₉-heteroaryl,wherein the number of hetero atoms from the group N, O, S may be from 1to 4, C₁-C₂₀-alkoxy, C₁-C₁₀-haloalkyl, hydroxy, amino of the formsNH—(C₁-C₂₀-alkyl), NH—(C₅-C₁₀-aryl), N(C₁-C₂₀-alkyl)₂,N(C₁-C₂₀-alkyl)(C₅-C₁₀-aryl), N(C₅-C₁₀-aryl)₂,N(C₁-C₂₀-alkyl/C₅-C₁₀-aryl₃)₃ ₊ , NH—CO—C₁-C₂₀-alkyl, NH—CO—C₅-C₁₀-aryl,carboxylato of the forms COOH and COOQ (wherein Q represents either amonovalent cation or C₁-C₈-alkyl), C₁-C₆-acyloxy, sulfinato, sulfonatoof the forms SO₃H and SO₃Q′ (wherein Q′ represents either a monovalentcation, C₁-C₂₀-alkyl, or C₅-C₁₀-aryl), tri-C₁-C₆-alkylsilyl, wherein twoof the mentioned substituents may also be bridged with one another,R^(2″)-R^(9″) represent a hydrogen, alkyl, alkenyl, cycloalkyl, aromaticor heteroaromatic aryl, O-alkyl, NH-alkyl, N-(alkyl)₂, O-(aryl),NH-(aryl), N-(alkyl)(aryl), O—CO-alkyl, O—CO-aryl, F, Si(alkyl)₃, CF₃,CN, CO₂H, COH, SO₃H, CONH₂, CONH(alkyl), CON(alkyl)₂, SO₂(alkyl),SO(alkyl), SO(aryl), SO₂(aryl), SO₃(alkyl), SO₃(aryl), S-alkyl, S-aryl,NH—CO(alkyl), CO₂(alkyl), CONH₂, CO(alkyl), NHCOH, NHCO₂(alkyl),CO(aryl), CO₂(aryl) radical, wherein two or more adjacent radicals, eachindependently of the other (s), may also be linked to one another sothat a condensed ring system is present and wherein in R^(2″) to R^(9″)alkyl represents a hydrocarbon radical having from 1 to 20 carbon atomswhich may in each case be linear or branched, alkenyl represents amono-or poly-unsaturated hydrocarbon radical having from 2 to 20 carbonatoms which may in each case be linear or branched, cycloalkylrepresents a hydrocarbon having from 3 to 20 carbon atoms, arylrepresents a 5- to 14-membered aromatic radical, wherein from one tofour carbon atoms in the aryl radical may also be replaced by heteroatoms from the group nitrogen, oxygen and sulfur so that a 5- to14-membered heteroaromatic radical is present, wherein the radicalsR^(2″) to R^(9″) may also carry further substituents as defined forR^(1″).

The organic phosphines and their synthesis are described inWO2004101581.

Preferred organic phosphines are selected from trisubstituted phosphinesof formula

Cpd. R^(1″) R^(5″) R^(6″) R^(3″) R^(4″) A-1 

H H H H A-2  cyclohexyl H H H H A-3  phenyl H H H H A-4  adamantyl H H HH A-5  cyclohexyl —OCH₃ H H H A-6  cyclohexyl ¹⁾ ¹⁾ H H A-7 

¹⁾ ¹⁾ H H A-8  phenyl ¹⁾ ¹⁾ H H A-9  adamantyl ¹⁾ ¹⁾ H H A-10 cyclohexylH H ²⁾ ²⁾ A-11

H H ²⁾ ²⁾ A-12 phenyl H H ²⁾ ²⁾ A-13 adamantyl H H ²⁾ ²⁾

Examples of preferred catalysts include the following compounds:

palladium(II) acetylacetonate, palladium(0) dibenzylidene-acetonecomplexes, palladium(II) propionate,

Pd₂(dba)₃: [tris(dibenzylideneacetone) dipalladium(0)],

Pd(dba)₂: [bis(dibenzylideneacetone) palladium(0)],

Pd(PR₃)₂, wherein PR₃ is a trisubstituted phosphine of formula VI,

Pd(OAc)₂: [palladium(II) acetate], palladium(II) chloride, palladium(II)bromide, lithium tetrachloropalladate(II),

PdCl₂(PR₃)₂; wherein PR₃ is a trisubstituted phosphine of formula VI;palladium(0) diallyl ether complexes, palladium(II) nitrate,

PdCl₂(PhCN)₂: [dichlorobis(benzonitrile) palladium(II)],

PdCl₂(CH₃CN): [dichlorobis(acetonitrile) palladium(II)], and

PdCl₂(COD): [dichloro(1,5-cyclooctadiene) palladium(II)].

Especially preferred are PdCl₂, Pd₂(dba)₃, Pd(dba)₂, Pd(OAc)₂, orPd(PR₃)₂. Most preferred are Pd₂(dba)₃ and Pd(OAc)₂.

The palladium catalyst is present in the reaction mixture in catalyticamounts. The term “catalytic amount” refers to an amount that is clearlybelow one equivalent of the (hetero)aromatic compound(s), preferably0.001 to 5 mol-%, most preferably 0.001 to 1 mol-%, based on theequivalents of the (hetero)aromatic compound(s) used.

The amount of phosphines or phosphonium salts in the reaction mixture ispreferably from 0.001 to 10 mol-%, most preferably 0.01 to 5 mol-%,based on the equivalents of the (hetero)aromatic compound(s) used. Thepreferred ratio of Pd:phosphine is 1:4.

The base can be selected from all aqueous and nonaqueous bases and canbe inorganic, or organic. It is preferable that at least 1.5 equivalentsof said base per functional boron group is present in the reactionmixture. Suitable bases are, for example, alkali and alkaline earthmetal hydroxides, carboxylates, carbonates, fluorides and phosphatessuch as sodium and potassium hydroxide, acetate, carbonate, fluoride andphosphate or also metal alcoholates. It is also possible to use amixture of bases. The base is preferably a lithium salt, such as, forexample, lithium alkoxides (such as, for example, lithium methoxide andlithium ethoxide), lithium hydroxide, carboxylate, carbonate, fluorideand/or phosphate.

The at present most preferred base is aqueous LiOHxH₂O (monohydrate ofLiOH) and (waterfree) LiOH.

The reaction is typically conducted at about 0° C. to 180° C.,preferably from 20 to 160° C., more preferably from 40 to 140° C. andmost preferably from 40 to 120° C. A polymerization reaction may take0.1, especially 0.2 to 100 hours.

In a preferred embodiment of the present invention the solvent istetrahydrofuran (THF), the base is LiOH*H20 and the reaction isconducted at reflux temperature of THF (about 65° C.).

The solvent is for example selected from toluene, xylenes, anisole, THF,2-methyltetrahydrofuran, dioxane, chlorobenzene, fluorobenzene orsolvent mixtures comprising one or more solvents like e.g. THF/tolueneand optionally water. Most preferred is THF, or THF/water.

Advantageously, the polymerisation is carried out in presence of

a) palladium(II) acetate, or Pd₂(dba)₃,(tris(dibenzylideneacetone)dipalladium(0)) and an organic phosphine A-1to A-13,

b) LiOH, or LiOHxH₂O; and

c) THF, and optionally water. If the monohydrate of LiOH is used, nowater needs to be added. The palladium catalyst is present in an amountof preferably about 0.5 mol-%, based on the equivalents of the(hetero)aromatic compound(s) used. The amount of phosphines orphosphonium salts in the reaction mixture is preferably about 2 mol-%,based on the equivalents of the (hetero)aromatic compound(s) used. Thepreferred ratio of Pd:phosphine is about 1:4.

Preferably the polymerization reaction is conducted under inertconditions in the absence of oxygen. Nitrogen and more preferably argonare used as inert gases.

The process described in WO2010/136352 is suitable for large-scaleapplications, is readily accessible and convert starting materials tothe respective polymers in high yield, with high purity and highselectivity. The process can provide polymers having weight averagemolecular weights of at least 10,000, more preferably at least 20,000,most preferably at least 30,000. The at present most preferred polymershave a weight average molecular weight of 30,000 to 80,000 Daltons.Molecular weights are determined according to high-temperature gelpermeation chromatography (HT-GPC) using polystyrene standards. Thepolymers preferably have a polydispersibility of 1.01 to 10, morepreferably 1.1 to 3.0, most preferred 1.5 to 2.5.

If desired, a monofunctional aryl halide or aryl boronate, such as, forexample,

may be used as a chain-terminator in such reactions, which will resultin the formation of a terminal aryl group.

It is possible to control the sequencing of the monomeric units in theresulting copolymer by controlling the order and composition of monomerfeeds in the Suzuki reaction.

The polymers of the present invention can also be sythesized by theStille coupling (see, for example, Babudri et al, J. Mater. Chem., 2004,14, 11-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508). Toprepare polymers corresponding to formula III a dihalogenide of formulaX¹⁰-A-X¹⁰ is reacted with a compound of formula X¹¹′—COM¹-X^(11′), or adihalogenide of formula X¹⁰—COM¹—X¹⁰ is reacted with a compound offormula X^(11′)-A-X^(11′), wherein X^(11′) is a group —SnR²⁰⁷R²⁰⁸R²⁰⁹and x¹⁰ is as defined above, in an inert solvent at a temperature inrange from 0° C. to 200° C. in the presence of a palladium-containingcatalyst, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or different and areH or C₁-C₆alkyl, wherein two radicals optionally form a common ring andthese radicals are optionally branched or unbranched. It must be ensuredhere that the totality of all monomers used has a highly balanced ratioof organotin functions to halogen functions. In addition, it may proveadvantageous to remove any excess reactive groups at the end of thereaction by end-capping with monofunctional reagents. In order to carryout the process, the tin compounds and the halogen compounds arepreferably introduced into one or more inert organic solvents andstirred at a temperature of from 0 to 200° C., preferably from 30 to170° C. for a period of from 1 hour to 200 hours, preferably from 5hours to 150 hours. The crude product can be purified by methods knownto the person skilled in the art and appropriate for the respectivepolymer, for example repeated re-precipitation or even by dialysis.

Suitable organic solvents for the process described are, for example,ethers, for example diethyl ether, dimethoxyethane, diethylene glycoldimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl etherand tert-butyl methyl ether, hydrocarbons, for example hexane,isohexane, heptane, cyclohexane, benzene, toluene and xylene, alcohols,for example methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol,1-butanol, 2-butanol and tert-butanol, ketones, for example acetone,ethyl methyl ketone and isobutyl methyl ketone, amides, for exampledimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone,nitriles, for example acetonitrile, propionitrile and butyronitrile, andmixtures thereof.

The palladium and phosphine components should be selected analogously tothe description for the Suzuki variant.

Alternatively, the polymers of the present invention can also besynthesized by the Negishi reaction using a zinc reagent A-(ZnX¹²)₂,wherein X¹² is halogen and halides, and COM¹-(X²³)₂, wherein X²³ ishalogen or triflate, or using A-(X²³)₂ and COM¹-(ZnX²³)₂. Reference is,for example, made to E. Negishi et al., Heterocycles 18 (1982) 117-22.

Alternatively, the polymers of the present invention can also besynthesized by the Hiyama reaction using a organosilicon reagentA-(SiR²¹⁰R²¹¹R²¹²)₂, wherein R²¹⁰, R²¹¹ and R²¹² are identical ordifferent and are halogen, or C₁-C₆alkyl, and COM¹-(X²³)₂, wherein X²³is halogen or triflate, or using A-(X²³)₂ and COM¹-(SiR²¹⁰R²¹¹R²¹²)₂.Reference is, for example, made to T. Hiyama et al., Pure Appl. Chem. 66(1994) 1471-1478 and T. Hiyama et al., Synlett (1991) 845-853.

Homopolymers of the type (A)_(n) can be obtained via Yamamoto couplingof dihalides X¹⁰-A-X¹⁰, where X¹⁰ is halogen, preferably Br.Alternatively homopolymers of the type (A)_(n) can be obtained viaoxidative polymerization of units X¹⁰-A-X¹⁰, where X¹⁰ is hydrogen, e.g.with FeCl₃ as oxidizing agent.

A possible synthesis route for monomers useful in the preparation ofpolymers, comprising repeating units of formula (I), wherein R¹ and R²are the same and are an optionally substituted C₆-C₂₄aryl, orC₂-C₂₀heteroaryl group; is shown below:

Compounds of formula (XVII) can be obtained by reacting compounds offormula (XX) with 1,4-dimethyl-piperazine-2,3-dione in the presence ofbutyl lithium in an appropriate solvent:

Compounds of formula (XVIII) can be obtained by reacting compounds offormula (XVII) with N-bromosuccinimide (NBS) in an appropriate solvent:

Intermediates for repeating units of formula (I), wherein R¹ and R² formtogether a group

can be obtained by reacting compounds of formula (XVIII) withcyclohex-2-en-1-one in the presence of TiCl₄ in dichloromethane atelevated temperatures.

Reference is, for example, made to WO2009115413.

The compounds of formula (VIII) and (IX) can be prepared by using theabove described intermediates and the synthesis methods described, forexample, in WO2012175530 and WO2010/115767.

The compounds of the formula

are intermediates in the production of polymers, are new and form afurther subject of the present invention. A^(1′) and A^(2′) areindependently of each other a group of formula

wherein X² and X^(2′) are independently of each other halogen, ZnX¹²,—SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or differentand are H or C₁-C₆alkyl, wherein two radicals optionally form a commonring and these radicals are optionally branched or unbranched and X¹² isa halogen atom; or —OS(O)₂CF₃, —OS(O)₂-aryl, —OS(O)₂CH₃, —B(OH)₂,—B(OY¹)₂,

—BF4Na, or —BF4K, wherein Y¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y² is independently in each occurrence aC₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—,wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y₈, Y⁹, Y¹⁰, Y¹¹ and Y₁₂ are independentlyof each other hydrogen, or a C₁-C₁₀alkyl group,

especially —C(CH₃)₂C(CH₃)₂—, —C(CH₃)₂CH₂C(CH₃)₂—, or —CH₂C(CH₃)₂CH₂—;and Y¹³ and Y¹⁴ are independently of each other hydrogen, or aC₁-C₁₀alkyl group. a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³,A⁴, A⁵ and A^(5′) are as defined above.

The compounds of the formula (IV), or (V) can be used in the productionof polymers, comprising repeating unit(s) of formula

wherein

A^(1′) and A^(2′) are independently of each other a group of formula

wherein a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, A⁴, A⁵ andA^(5′) are as defined above.

Halogen is fluorine, chlorine, bromine and iodine.

The C₁-C₁₀₀alkyl group is preferably a C₁-C₃₈alkyl group, especially aC₁-C₂₅alkyl group. Reference is made to the definition of R²⁰¹.

C₁-C₂₅alkyl (C₁-C₁₈alkyl) is typically linear or branched, wherepossible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl,1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl.C₁-C₈alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl,sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl,2,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl,1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C₁-C₄alkyl is typicallymethyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,tert.-butyl.

C₂-C₂₅alkenyl (C₂-C₁₈alkenyl) groups are straight-chain or branchedalkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl,2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl,3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl,n-dodec-2-enyl or n-octadec-4-enyl.

C₂₋₂₅alkynyl (C₂₋₁₈alkynyl) is straight-chain or branched and preferablyC₂₋₈alkynyl, which may be unsubstituted or substituted, such as, forexample, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl,2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl,1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl,trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl,1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

A halogenated C₁-C₂₅alkyl group is a branched or unbranched radical,wherein all, or part of the hydrogen atoms of the corresponding alkylgroup have been replaced by halogen atoms.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, besubstituted by any acyclic substituents, but are preferablyunsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkylthiogroups as exemplified further below. The term “aliphatic group”comprises also alkyl groups wherein certain non-adjacent carbon atomsare replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CH₃. The latter group canbe regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

An aliphatic hydrocarbon group having up to 25 carbon atoms is a linearor branched alkyl, alkenyl or alkynyl (also spelled alkinyl) grouphaving up to 25 carbon atoms as exemplified above.

Alkylene is bivalent alkyl, i.e. alkyl having two (instead of one) freevalencies, e.g. trimethylene or tetramethylene.

Alkenylene is bivalent alkenyl, i.e. alkenyl having two (instead of one)free valencies, e.g. —CH₂—CH═CH—CH₂—.

Aliphatic groups can, in contrast to aliphatic hydrocarbon groups, besubstituted by any acyclic substituents, but are preferablyunsubstituted. Preferred substituents are C₁-C₈alkoxy or C₁-C₈alkylthiogroups as exemplified further below. The term “aliphatic group”comprises also alkyl groups wherein certain non-adjacent carbon atomsare replaced by oxygen, like —CH₂—O—CH₂—CH₂—O—CH₃. The latter group canbe regarded as methyl substituted by —O—CH₂—CH₂—O—CH₃.

A cycloaliphatic hydrocarbon group is a cycloalkyl or cycloalkenyl groupwhich may be substituted by one or more aliphatic and/or cycloaliphatichydrocarbon groups.

A cycloaliphatic-aliphatic group is an aliphatic group substituted by acycloaliphatic group, wherein the terms “cycloaliphatic” and “aliphatic”have the meanings given herein and wherein the free valency extends fromthe aliphatic moiety. Hence, a cycloaliphatic-aliphatic group is forexample a cycloalkyl-alkyl group.

A cycloalkyl-alkyl group is an alkyl group substituted by a cycloalkylgroup, e.g. cyclohexyl-methyl.

A “cycloalkenyl group” means an unsaturated alicyclic hydrocarbon groupcontaining one or more double bonds, such as cyclopentenyl,cyclopentadienyl, cyclohexenyl and the like, which may be unsubstitutedor substituted by one or more aliphatic and/or cycloaliphatichydrocarbon groups and/or condensed with phenyl groups.

A bivalent group of the formula IVb wherein R²⁸ and R²⁷ togetherrepresent alkylene or alkenylene which may be both bonded via oxygenand/or sulfur to the thienyl residue and which may both have up to 25carbon atoms, is e.g. a group of the formula

wherein A²⁰ represents linear or branched alkylene having up to 25carbon atoms, preferably ethylene or propylene which may be substitutedby one or more alkyl groups, and Y²⁰ represents oxygen or sulphur. Forexample, the bivalent group of the formula —Y²⁰-A²⁰-O— represents—O—CH₂—CH₂—O— or —O—CH₂—CH₂—CH₂—O—.

A group of the formula IVa wherein two groups R²² to R²⁶ which are inthe neighborhood of each other, together represent alkylene oralkenylene having up to 8 carbon atoms, thereby forming a ring, is e.g.a group of the formula

wherein in the group of the formula XXXII R²³ and R²⁴ together represent1,4-butylene and in the group of the formula XXXIII R²³ and R²⁴ togetherrepresent 1,4-but-2-en-ylene.

The C₁-C₁₀₀alkoxy group is preferably a C₁-C₃₈alkoxy group, especially aC₁-C₂₅alkoxy group. C₁-C₂₅alkoxy groups (C₁-C₁₈alkoxy groups) arestraight-chain or branched alkoxy groups, e.g. methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy,isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy,decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy,hexadecyloxy, heptadecyloxy and octadecyloxy. Examples of C₁-C₈alkoxyare methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy,isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy,2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy,1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably C₁-C₄alkoxy suchas typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec.-butoxy, isobutoxy, tert.-butoxy. The term “alkylthio group” meansthe same groups as the alkoxy groups, except that the oxygen atom of theether linkage is replaced by a sulfur atom.

C₁-C₁₈fluoroalkyl, especially C₁-C₄fluoroalkyl, is a branched orunbranched radical, wherein all, or part of the hydrogen atoms of thecorresponding alkyl group have been replaced by fluorine atoms, such asfor example —CF₃, —CF₂CF₃, —CF₂CF₂CF₃, —CF(CF₃)₂, —(CF₂)₃CF₃, and—C(CF₃)₃.

The term “carbamoyl group” is typically a C₁₋₁₈carbamoyl radical,preferably C₁₋₈carbamoyl radical, which may be unsubstituted orsubstituted, such as, for example, carbamoyl, methylcarbamoyl,ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl,dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

A cycloalkyl group is typically C₄-C₁₈cycloalkyl, such as, for example,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl,cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted orsubstituted. The cycloalkyl group, in particular a cyclohexyl group, canbe condensed one or two times by phenyl which can be substituted one tothree times with C₁-C₄-alkyl, halogen and cyano. Examples of suchcondensed cyclohexyl groups are:

in particular

wherein R¹⁵¹, R¹⁵², R¹⁵³, R¹⁵⁴, R¹⁵⁵ and R¹⁵⁶ are independently of eachother C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen and cyano, in particularhydrogen.

C₆-C₂₄aryl (C₆-C₁₈aryl) is typically phenyl, indenyl, azulenyl,naphthyl, biphenyl, as-indacenyl, s-indacenyl, acenaphthylenyl,fluorenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl,naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, oranthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl,9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may beunsubstituted or substituted. Examples of C₆-C₁₂aryl are phenyl,1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or9-phenanthryl, which may be unsubstituted or substituted.

C₇-C₂₅aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl,α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl,ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl orω-phenyl-docosyl, preferably C₇-C₁₈aralkyl such as benzyl,2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl,ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, andparticularly preferred C₇-C₁₂aralkyl such as benzyl, 2-benzyl-2-propyl,β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, orω,ω-dimethyl-ω-phenyl-butyl, in which both the aliphatic hydrocarbongroup and aromatic hydrocarbon group may be unsubstituted orsubstituted. Preferred examples are benzyl, 2-phenylethyl,3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl.

Heteroaryl is typically C₂-C₂₀heteroaryl, i.e. a ring with five to sevenring atoms or a condensed ring system, wherein nitrogen, oxygen orsulfur are the possible hetero atoms, and is typically an unsaturatedheterocyclic group with five to 30 atoms having at least six conjugatedm-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl,thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl,isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl,pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl,pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl,quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl,chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl,carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl,pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl,isoxazolyl, furazanyl or phenoxazinyl, which can be unsubstituted orsubstituted.

Possible substituents of the above-mentioned groups are C₁-C₈alkyl, ahydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen,halo-C₁-C₈alkyl, a cyano group, a carbamoyl group, a nitro group or asilyl group, especially C₁-C₈alkyl, C₁-C₈alkoxy, C₁-C₈alkylthio,halogen, halo-C₁-C₈alkyl, or a cyano group.

C₁-C₂₅alkyl (C₁-C₁₈alkyl) interrupted by one or more O is, for example,(CH₂CH₂O)₁₋₉—R^(x), where R^(x) is H or C₁-C₁₀alkyl,CH₂—CH(OR^(y′))—CH₂—O—R^(y), where R^(y) is C₁-C₁₈alkyl, and R^(y′)embraces the same definitions as R^(y) or is H.

If a substituent, such as, for example R³, occurs more than one time ina group, it can be different in each occurrence.

The present invention also relates to the use of the polymers, orcompounds in an organic, electronic device.

The organic, electronic device is, for example, an organicelectroluminescent device (OLED), a polymeric electroluminescent device(PLED), an organic integrated circuit (O-IC), an organic field-effecttransistor (O-FET), an organic thin-film transistor (O-TFT), an organiclight-emitting transistor (O-LET), an organic solar cell (O-SC), anorganic optical detector, an organic photoreceptor, an organicfield-quench device (O-FQD), a light-emitting electrochemical cell(LEC), or an organic laser diode (O-laser).

For the purposes of the present invention, it is preferred for thepolymer, or compound according to the invention to be in the form of alayer (or to be present in a layer) in the electronic device. Thepolymer, or compound according to the invention can be present in theform of a hole-transport, hole-injection, emitter, electron-transport,electron-injection, charge-blocking and/or charge-generation layer. Thepolymers, or compounds according to the invention may be, for example,employed as emitting compounds in an emitting layer.

It may additionally be preferred to use the polymer not as the puresubstance, but instead as a mixture (blend) together with furtherpolymeric, oligomeric, dendritic or low-molecular-weight substances ofany desired type. These may, for example, improve the electronicproperties.

A mixture containing a polymer of the present invention results in asemi-conducting layer comprising a polymer of the present invention(typically 5% to 99.9999% by weight, especially 20 to 85% by weight) andat least another material. The other material can be, but is notrestricted to a fraction of the same polymer of the present inventionwith different molecular weight, another polymer of the presentinvention, a semi-conducting polymer, organic small molecules, carbonnanotubes, a fullerene derivative, inorganic particles (quantum dots,quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles(Au, Ag etc.), insulator materials like the ones described for the gatedielectric (PET, PS etc.). The polymers of the present invention can beblended with compounds of formula VIII, or IX according to the presentinvention, or small molecules described, for example, in WO2009/047104,WO2010108873, WO09/047104, U.S. Pat. No. 6,690,029, WO2007082584, andWO2008107089:

WO2007082584:

WO2008107089:

wherein one of Y^(1′) and Y^(2′) denotes —CH═ or ═CH— and the otherdenotes —X*—,

one of Y^(3′) and Y^(4′) denotes —CH═ or ═CH— and the other denotes—X*—,

X* is —O—, —S—, —Se— or —NR′″—,

R* is cyclic, straight-chain or branched alkyl or alkoxy having 1 to 20C-atoms, or aryl having 2-30 C-atoms, all of which are optionallyfluorinated or perfluorinated,

R′ is H, F, Cl, Br, I, CN, straight-chain or branched alkyl or alkoxyhaving 1 to 20 C-atoms and optionally being fluorinated orperfluorinated, optionally fluorinated or perfluorinated aryl having 6to 30 C-atoms, or CO₂R″, with R″ being H, optionally fluorinated alkylhaving 1 to 20 C-atoms, or optionally fluorinated aryl having 2 to 30C-atoms,

R′″ is H or cyclic, straight-chain or branched alkyl with 1 to 10C-atoms, y is 0, or 1, x is 0, or 1.

The polymer can contain a small molecule, or a mixture of two, or moresmall molecule compounds.

Accordingly, the present invention also relates to an organicsemiconductor material, layer or component, comprising a polymeraccording to the present invention.

The polymers of the invention can be used as the semiconductor layer insemiconductor devices. Accordingly, the present invention also relatesto semiconductor devices, comprising a polymer of the present invention,or an organic semiconductor material, layer or component. Thesemiconductor device is especially an organic photovoltaic (PV) device(solar cell), a photodiode, or an organic field effect transistor.

The polymers of the invention can be used alone or in combination as theorganic semiconductor layer of the semiconductor device. The layer canbe provided by any useful means, such as, for example, vapor deposition(for materials with relatively low molecular weight) and printingtechniques. The compounds of the invention may be sufficiently solublein organic solvents and can be solution deposited and patterned (forexample, by spin coating, dip coating, ink jet printing, gravureprinting, flexo printing, offset printing, screen printing, microcontact(wave)-printing, drop or zone casting, or other known techniques).

The polymers of the invention can be used in integrated circuitscomprising a plurality of OTFTs, as well as in various electronicarticles. Such articles include, for example, radio-frequencyidentification (RFID) tags, backplanes for flexible displays (for usein, for example, personal computers, cell phones, or handheld devices),smart cards, memory devices, sensors (e.g. light-, image-, bio-, chemo-,mechanical- or temperature sensors), especially photodiodes, or securitydevices and the like.

A further aspect of the present invention is an organic semiconductormaterial, layer or component comprising one or more polymers of thepresent invention. A further aspect is the use of the polymers ormaterials of the present invention in an organic photovoltaic (PV)device (solar cell), a photodiode, or an organic field effect transistor(OFET). A further aspect is an organic photovoltaic (PV) device (solarcell), a photodiode, or an organic field effect transistor (OFET)comprising a polymer or material of the present invention.

The polymers of the present invention are typically used as organicsemiconductors in form of thin organic layers or films, preferably lessthan 30 microns thick. Typically the semiconducting layer of the presentinvention is at most 1 micron (=1 μm) thick, although it may be thickerif required. For various electronic device applications, the thicknessmay also be less than about 1 micron thick. For example, for use in anOFET the layer thickness may typically be 100 nm or less. The exactthickness of the layer will depend, for example, upon the requirementsof the electronic device in which the layer is used.

For example, the active semiconductor channel between the drain andsource in an OFET may comprise a layer of the present invention.

An OFET device according to the present invention preferably comprises:

-   -   a source electrode,    -   a drain electrode,    -   a gate electrode,    -   a semiconducting layer,    -   one or more gate insulator layers, and    -   optionally a substrate, wherein the semiconductor layer        comprises one or more polymers of the present invention.

The gate, source and drain electrodes and the insulating andsemiconducting layer in the OFET device may be arranged in any sequence,provided that the source and drain electrode are separated from the gateelectrode by the insulating layer, the gate electrode and thesemiconductor layer both contact the insulating layer, and the sourceelectrode and the drain electrode both contact the semiconducting layer.

Preferably the OFET comprises an insulator having a first side and asecond side, a gate electrode located on the first side of theinsulator, a layer comprising a polymer of the present invention locatedon the second side of the insulator, and a drain electrode and a sourceelectrode located on the polymer layer.

The OFET device can be a top gate device or a bottom gate device.

Suitable structures and manufacturing methods of an OFET device areknown to the person skilled in the art and are described in theliterature, for example in W003/052841.

The gate insulator layer may comprise for example a fluoropolymer, likee.g. the commercially available Cytop 809M®, or Cytop 107M® (from AsahiGlass). Preferably the gate insulator layer is deposited, e.g. byspin-coating, doctor blading, wire bar coating, spray or dip coating orother known methods, from a formulation comprising an insulator materialand one or more solvents with one or more fluoro atoms (fluorosolvents),preferably a perfluorosolvent. A suitable perfluorosolvent is e.g. FC₇₅®(available from Acros, catalogue number 12380). Other suitablefluoropolymers and fluorosolvents are known in prior art, like forexample the perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont), orFluoropel® (from Cytonix) or the perfluorosolvent FC 43® (Acros, No.12377).

The semiconducting layer comprising a polymer of the present inventionmay additionally comprise at least another material. The other materialcan be, but is not restricted to another polymer of the presentinvention, a semi-conducting polymer, a polymeric binder, organic smallmolecules different from a polymer of the present invention, carbonnanotubes, a fullerene derivative, inorganic particles (quantum dots,quantum rods, quantum tripods, TiO₂, ZnO etc.), conductive particles(Au, Ag etc.), and insulator materials like the ones described for thegate dielectric (PET, PS etc.). As stated above, the semiconductivelayer can also be composed of a mixture of one or more polymers of thepresent invention and a polymeric binder. The ratio of the polymers ofthe present invention to the polymeric binder can vary from 5 to 95percent. Preferably, the polymeric binder is a semicristalline polymersuch as polystyrene (PS), high-density polyethylene (HDPE),polypropylene (PP) and polymethylmethacrylate (PMMA). With thistechnique, a degradation of the electrical performance can be avoided(cf. WO2008/001123A1).

The polymers of the present invention are advantageously used in organicphotovoltaic (PV) devices (solar cells). Accordingly, the inventionprovides PV devices comprising a polymer according to the presentinvention. A device of this construction will also have rectifyingproperties so may also be termed a photodiode. Photoresponsive deviceshave application as solar cells which generate electricity from lightand as photodetectors which measure or detect light.

The PV device comprise in this order:

(a) a cathode (electrode),

(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) an anode (electrode),

(f) a substrate.

The photoactive layer comprises the polymers of the present invention.Preferably, the photoactive layer is made of a conjugated polymer of thepresent invention, as an electron donor and an acceptor material, like afullerene, particularly a functionalized fullerene PCBM, as an electronacceptor. As stated above, the photoactive layer may also contain apolymeric binder. The ratio of the polymers of formula I to thepolymeric binder can vary from 5 to 95 percent. Preferably, thepolymeric binder is a semicristalline polymer such as polystyrene (PS),high-density polyethylene (HDPE), polypropylene (PP) andpolymethylmethacrylate (PMMA).

For heterojunction solar cells the active layer comprises preferably amixture of a polymer of the present invention and a fullerene, such as,for example, [60]PCBM (=6,6-phenyl-C₆₁-butyric acid methyl ester), or[70]PCBM, in a weight ratio of 1:1 to 1:3. The fullerenes useful in thisinvention may have a broad range of sizes (number of carbon atoms permolecule). The term fullerene as used herein includes various cage-likemolecules of pure carbon, including Buckminsterfullerene (C₆₀) and therelated “spherical” fullerenes as well as carbon nanotubes. Fullerenesmay be selected from those known in the art ranging from, for example,C₂₀-C₁₀₀₀. Preferably, the fullerene is selected from the range of C₆₉to C₉₆. Most preferably the fullerene is C₆₉ or CM, such as [60]PCBM, or[70]PCBM. It is also permissible to utilize chemically modifiedfullerenes, provided that the modified fullerene retains acceptor-typeand electron mobility characteristics. The acceptor material can also bea material selected from the group consisting of any semi-conductingpolymer, such as, for example, a polymer of the present invention,provided that the polymers retain acceptor-type and electron mobilitycharacteristics, organic small molecules, carbon nanotubes, inorganicparticles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.).

The photoactive layer is made of a polymer of the present invention asan electron donor and a fullerene, particularly functionalized fullerenePCBM, as an electron acceptor. These two components are mixed with asolvent and applied as a solution onto the smoothing layer by, forexample, the spin-coating method, the drop casting method, theLangmuir-Blodgett (“LB”) method, the ink jet printing method and thedripping method. A squeegee or printing method could also be used tocoat larger surfaces with such a photoactive layer. Instead of toluene,which is typical, a dispersion agent such as chlorobenzene is preferablyused as a solvent. Among these methods, the vacuum deposition method,the spin-coating method, the ink jet printing method and the castingmethod are particularly preferred in view of ease of operation and cost.

In the case of forming the layer by using the spin-coating method, thecasting method and ink jet printing method, the coating can be carriedout using a solution and/or dispersion prepared by dissolving, ordispersing the composition in a concentration of from 0.01 to 90% byweight in an appropriate organic solvent such as benzene, toluene,xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide,acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide,chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

The photovoltaic (PV) device can also consist of multiple junction solarcells that are processed on top of each other in order to absorb more ofthe solar spectrum. Such structures are, for example, described in App.Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006)and WO2004/112161.

A so called ‘tandem solar cell’ comprise in this order:

(a) a cathode (electrode),

(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) a middle electrode (such as Au, Al, ZnO, TiO₂ etc.)

(f) optionally an extra electrode to match the energy level,

(g) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,

(h) a photoactive layer,

(i) optionally a smoothing layer,

(j) an anode (electrode),

(k) a substrate.

The PV device can also be processed on a fiber as described, forexample, in US20070079867 and US 20060013549.

Due to their excellent self-organising properties the materials or filmscomprising the polymers of the present invention can also be used aloneor together with other materials in or as alignment layers in LCD orOLED devices, as described for example in US2003/0021913.

It is another object of the present invention to provide compounds,which show high efficiency of energy conversion, excellent field-effectmobility, good on/off current ratios and/or excellent stability, whenused in organic field effect transistors, organic photovoltaics (solarcells) and photodiodes.

In a further embodiment the present invention relates to compounds ofthe formula

wherein Y, Y¹⁵, Y¹⁶ and Y¹⁷ are independently of each other a group offormula

wherein R¹, R², R⁶⁰¹ and R⁶⁰² are as defined above,

p is 0, or 1, q is 0, or 1;

A¹ and A² are independently of each other a group of formula

a is 0, 1, 2, or 3, b is 0, 1, 2, or 3; c is 0, 1, 2, or 3;

A³, A⁴, A⁵ and A^(5′) are independently of each other a group of formula

—[Ar⁴]_(k)—[Ar⁵]_(l)—[Ar⁶]_(r)—[Ar⁷]_(z)—;

k′ is 0, 1, 2, or 3; l is 0, 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1,2, or 3;

R¹⁰ is hydrogen, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which issubstituted one or more times by E″ and/or interrupted one or more timesby D″,

COO—C₁-C₁₈alkyl, C₄-C₁₈cycloalkyl group, C₄-C₁₈cycloalkyl group, whichis substituted by G″, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈thioalkoxy,C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E″ and/or interruptedby D″, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl, which is substituted by G″, or agroup of formulae IVa to IVm,

wherein R²² to R²⁶ and R²⁹ to R⁵⁸ represent independently of each otherH, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E″and/or interrupted by D″, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted byG″, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G″, aC₄-C₁₈cycloalkyl group, a C₄-C₁₈cycloalkyl group, which is substitutedby G″, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E″ and/or interrupted by D″, C₇-C₂₅aralkyl, orC₇-C₂₅aralkyl, which is substituted by G″,

R²⁷ and R²⁸ are independently of each other hydrogen, C₁-C₂₅alkyl,halogen, cyano or C₇-C₂₅aralkyl, or R²⁷ and R²⁸ together representalkylene or alkenylene which may be both bonded via oxygen and/or sulfurto the thienyl residue and which may both have up to 25 carbon atoms,

R⁵⁹ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl,

D″ is —CO—, —COO—, —S—, —O—, or NR^(112″)—,

E″ is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR^(112″)R^(113″),—CONR^(112″)R^(113″), or halogen,

G″ is E″, or C₁-C₁₈alkyl, and

R^(112″) and R^(113″) are independently of each other H; C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—;

R²¹⁴ and R²¹⁵ are independently of each other hydrogen, C₁-C₁₈alkyl,C₆-C₂₄aryl, C₂-C₂₀heteroaryl, —CN or COOR²¹⁶;

R²¹⁶ is C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₇-C₂₅arylalkyl, C₆-C₂₄aryl orC₂-C₂₀heteroaryl;

R²¹⁸ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted byC₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl,

Ar¹, Ar², Ar³ Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are independently of each other agroup of formula (XIa), (XIb), (XIc), (XId), (XIe), (XIf), (XIg), (XIh),(XIi), (XIj), (XIk), (XIl), (XIm), (XIn), (XIo), (XIpa), (XIpb), (XIq),(XIr), (XIs), (XIt), (XIu), (XIv), (XIw), (XIx), (XIy), (XIz), (XIIa),(XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj),(XIIk), (XIII), such as, for example, (XIIIa), (XIIIb), (XIIIc),(XIIId), (XIIIe), (XIIIf), (XIIIg), (XIIIh), (XIIIi), (XIIIj), (XIIIk),and (XIIIl); or (XIV), such as, for example, (XIVa); (XVa), (XVb),(XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl),(XVm), (XVn), (XVo), (XVp), (XVq), (XVr), (XVs), such as, for example,(XVsa), (XVsb), and (XVsc); (XVt), such as, for example, (XVta), (XVtb),and (XVuc), and (XVu).

The structure represented by formula

can be bonded in two ways to the groups of formula A³, A⁴, A⁵ andA^(5′):

(the dotted line represents the bonding to the groups of formula A³, A⁴,A⁵ and A^(5′)). Both possibilities shall be covered by formula (I).

Preferably, the compound is a compound of the formula A¹-Y-A³-Y¹⁵-A²(VIIIa), A¹-Y-A³-Y¹⁵-A⁴-Y¹⁶-A² (VIIIb),or A¹-Y-A³-Y¹⁵-A⁴-Y¹⁶-A⁵-Y¹⁷-A²(VIIIc), A¹-A³-Y-A⁴-A² (IXa), A¹-A³-Y-A⁴-Y¹⁵-A⁵-A² (IXb), orA¹-A³-Y-A⁴-Y₁₅-A⁵-Y¹⁷-A^(5′)-A² (IXc), wherein Y, Y¹⁵, Y¹⁶ and Y¹⁷ areindependently of each other a group of formula

wherein R¹ and R² are independently of each other a group of formula

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are independently of eachother H, CN, F, CF₃, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—, or

R¹ and R² form together a group

and R⁶⁰¹ and R⁶⁰² are independently of each other hydrogen, or C₁-C₂₅alkyl, especially hydrogen.

A¹ and A² are as defined above,

A³, A⁴, A⁵ and A^(5′) are independently of each other a group of formula

wherein

R³, R^(3′), R⁴ and R^(4′) are independently of each other hydrogen, orC₁-C₂₅alkyl;

R⁸ and R^(8′) are independently of each other hydrogen, or C₁-C₂₅alkyl;

R¹¹⁴ is a C₁-C₃₈alkyl group;

R²⁰¹ is a C₁-C₃₈alkyl group; and

R²⁰² and R^(203′) are independently of each other hydrogen orC₁-C₂₅alkyl.

R¹ and R² are especially a group of formula

very especially a group of formula

R¹ and R² may be the same, but are preferably the same.

The group of formula (I) is preferably a group of formula

especially (Ia).

In a preferred embodiment A³, A⁴, A⁵ and A^(5′) are independently ofeach other a group of formula (XVb), (XVb′), (XVh), (XVh′), (XVi),(XVi′), (XVu′) , (XVu″), and (XVu′″). In a particularly preferredembodiment A³, A⁴, A⁵ and A^(5′) are selected from groups of formula(XVb), (XVc), (XVu′), (XVu″), and (XVu′″).

In a preferred embodiment of the present invention A¹ and A² areindependently of each other a group of formula H,

In a preferred embodiment the present invention is directed to compoundsof formula A¹-A³-Y-A⁴-A² (IXa), wherein Y is a group of formula

In said embodiment A¹-A³- and A⁴-A²- are a group of formula:

i)

(R³ and R⁴ may be different, but are preferably the same and are H, orC₁-C₂₅alkyl; R²⁰¹ is a C₁-C₃₈alkyl group);

ii)

(R³ and R⁴ may be different, but are preferably the same and are H, orC₁-C₂₅alkyl; R²⁰¹ is a C₁-C₃₈alkyl group);

iii)

(R³ and R^(3′) may be different, but are preferably the same and are H,or C₁-C₂₅alkyl; R⁴ and R^(4′) may be different, but are preferably thesame and are H, or C₁-C₂₅alkyl).

Examples of particular preferred compounds of formula IX are shownbelow:

wherein R³, R^(3′), R⁴ and R^(4′) are independently of each otherhydrogen or C₁-C₂₅alkyl; and R²⁰¹ is a C₁-C₃₈alkyl group. R³, R^(3′), R⁴and R^(4′) are preferably hydrogen.

Compounds A-1, A-2, A-5 and A-11 are most preferred.

A¹-A³-Y-A³-A¹ (IXa) may be prepared by reacting a compound of formulaAl-A³-X¹⁶ with a compound of formula X^(16′)—Y—X^(16′), X^(16′) is—B(OH)₂, —B(OH)₃—, —BF₃, —B(OY¹)₂,

and X¹⁶ is halogen, such as, for example, Br, or I.

The Suzuki reaction is typically conducted at about 0° C. to 180° C. inan aromatic hydrocarbon solvent such as toluene, xylene. Other solventssuch as dimethylformamide, dioxane, dimethoxyethan and tetrahydrofurancan also be used alone, or in mixtures with an aromatic hydrocarbon. Anaqueous base, preferably sodium carbonate or bicarbonate, potassiumphosphate, potassium carbonate or bicarbonate is used as activationagent for the boronic acid, boronate and as the HBr scavenger. Acondensation reaction may take 0.2 to 100 hours. Organic bases, such as,for example, tetraalkylammonium hydroxide, and phase transfer catalysts,such as, for example TBAB, can promote the activity of the boron (see,for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003)1407 and references cited therein). Other variations of reactionconditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59(1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol.Rapid Commun. 17 (1996) 239-252.

In the above Suzuki coupling reactions the halogen X¹⁶ on thehalogenated reaction partner can be replaced with the X^(16′) moiety andat the same time the X^(16′) moiety of the other reaction partner isreplaced by X¹⁶.

The synthesis of the corresponding diketopyrrolopyrrole intermediatesis, for example, described in R. A. J. Janssen et al., Macromol. Chem.Phys. 2011, 212, 515-520, US2010/0326225 and EP11179840.1.

Accordingly, the present invention also relates to an organicsemiconductor material, layer or component, comprising a compound offormula VIII, or IX and to a semiconductor device, comprising a compoundof formula VIII, or IX and/or an organic semiconductor material, layeror component.

The semiconductor is preferably an organic photovoltaic (PV) device(solar cell), a photodiode, or an organic field effect transistor. Thestructure and the components of the OFET device has been described inmore detail above.

Accordingly, the invention provides organic photovoltaic (PV) devices(solar cells) comprising a compound of the formula VIII, or IX.

The structure of organic photovoltaic devices (solar cells) is, forexample, described in C. Deibel et al. Rep. Prog. Phys. 73 (2010) 096401and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.

The PV device comprise in this order:

(a) a cathode (electrode),

(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) an anode (electrode),

(f) a substrate.

The photoactive layer comprises the compounds of the formula VIII, orIX. Preferably, the photoactive layer is made of a compound of theformula VIII, or IX, as an electron donor and an acceptor material, likea fullerene, particularly a functionalized fullerene PCBM, as anelectron acceptor. As stated above, the photoactive layer may alsocontain a polymeric binder. The ratio of the small molecules of formulaVIII, or IX to the polymeric binder can vary from 5 to 95 percent.Preferably, the polymeric binder is a semicristalline polymer such aspolystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP)and polymethylmethacrylate (PMMA).

The fullerenes useful in this invention may have a broad range of sizes(number of carbon atoms per molecule). The term fullerene as used hereinincludes various cage-like molecules of pure carbon, includingBuckminsterfullerene (C₆₀) and the related “spherical” fullerenes aswell as carbon nanotubes. Fullerenes may be selected from those known inthe art ranging from, for example, C₂₀-C₁₀₀₀. Preferably, the fullereneis selected from the range of C₆₉ to C₉₆. Most preferably the fullereneis C₆₉ or C₇₀, such as [60]PCBM, or [70]PCBM. It is also permissible toutilize chemically modified fullerenes, provided that the modifiedfullerene retains acceptor-type and electron mobility characteristics.The acceptor material can also be a material selected from the groupconsisting of another compounds of formula VIII, or IX, or anysemi-conducting polymer, such as, for example, a polymer of formula I,provided that the polymers retain acceptor-type and electron mobilitycharacteristics, organic small molecules, carbon nanotubes, inorganicparticles (quantum dots, quantum rods, quantum tripods, TiO₂, ZnO etc.).

The photoactive layer is made of a compound of the formula VIII, or IX,as an electron donor and a fullerene, particularly functionalizedfullerene PCBM, as an electron acceptor. These two components are mixedwith a solvent and applied as a solution onto the smoothing layer by,for example, the spin-coating method, the drop casting method, theLangmuir-Blodgett (“LB”) method, the ink jet printing method and thedripping method. A squeegee or printing method could also be used tocoat larger surfaces with such a photoactive layer. Instead of toluene,which is typical, a dispersion agent such as chlorobenzene is preferablyused as a solvent. Among these methods, the vacuum deposition method,the spin-coating method, the ink jet printing method and the castingmethod are particularly preferred in view of ease of operation and cost.

In the case of forming the layer by using the spin-coating method, thecasting method and ink jet printing method, the coating can be carriedout using a solution and/or dispersion prepared by dissolving, ordispersing the composition in a concentration of from 0.01 to 90% byweight in an appropriate organic solvent such as benzene, toluene,xylene, tetrahydrofurane, methyltetrahydrofurane, N,N-dimethylformamide,acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide,chlorobenzene, 1,2-dichlorobenzene and mixtures thereof.

The photovoltaic (PV) device can also consist of multiple junction solarcells that are processed on top of each other in order to absorb more ofthe solar spectrum. Such structures are, for example, described in App.Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006)and WO2004/112161.

A so called ‘tandem solar cell’ comprise in this order:

(a) a cathode (electrode),

(b) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,

(c) a photoactive layer,

(d) optionally a smoothing layer,

(e) a middle electrode (such as Au, Al, ZnO, TiO₂ etc.)

(f) optionally an extra electrode to match the energy level,

(g) optionally a transition layer, such as an alkali halogenide,especially lithium fluoride,

(h) a photoactive layer,

(i) optionally a smoothing layer,

(j) an anode (electrode),

(k) a substrate.

The PV device can also be processed on a fiber as described, forexample, in US20070079867 and US 20060013549.

Due to their excellent self-organising properties the materials or filmscomprising the compounds of the formula VIII, or IX can also be usedalone or together with other materials in or as alignment layers in LCDor OLED devices, as described for example in US2003/0021913.

An OFET device according to the present invention preferably comprises:

-   -   a source electrode,    -   a drain electrode,    -   a gate electrode,    -   a semiconducting layer,    -   one or more gate insulator layers, and    -   optionally a substrate, wherein the semiconductor layer        comprises a compound of formula VIII, or IX.

The gate, source and drain electrodes and the insulating andsemiconducting layer in the OFET device may be arranged in any sequence,provided that the source and drain electrode are separated from the gateelectrode by the insulating layer, the gate electrode and thesemiconductor layer both contact the insulating layer, and the sourceelectrode and the drain electrode both contact the semiconducting layer.

Preferably the OFET comprises an insulator having a first side and asecond side, a gate electrode located on the first side of theinsulator, a layer comprising a compound of formula VIII, or IX locatedon the second side of the insulator, and a drain electrode and a sourceelectrode located on the polymer layer.

The following examples are included for illustrative purposes only anddo not limit the scope of the claims. Unless otherwise stated, all partsand percentages are by weight. Weight-average molecular weight (Mw) andpolydispersity (Mw/Mn=PD) are determined by High Temperature GelPermeation Chromatography (HT-GPC) [Apparatus: GPC PL 220 from AgilentTechnologies (Santa Clara, Calif., USA) yielding the responses fromrefractive index (RI), Chromatographic conditions: Column: 3 “PLgelMixed B” columns from Agilent Technologies (Santa Clara, Calif., USA);with an average particle size of 10 □μm (dimensions 300×7.5 mm I.D.)Mobile phase: 1,2,4-trichlorobenzene (for GPC, AppliChem, Darmstadt,Germany) stabilised by butylhydroxytoluene (BHT, 1 g/l), Chromatographictemperature: 150° C.; Mobile phase flow: 1 ml/min; Solute concentration:about 1 mg/ml; Injection volume: 200 μl; Detection: RI, Procedure ofmolecular weight calibration: Relative calibration is done by use of aEasiVial calibration kit from Agilent Technologies (Santa Clara, Calif.,USA) containing 12 narrow polystyrene calibration standards spanning themolecular weight range from 6,035,000 Da-162 Da, i. e., PS 6,035,000, PS3,053,000, PS 915,000, PS 483,000, PS 184,900, PS 60,450, PS 19,720, PS8,450, PS 3,370, PS 1,260, PS 580, PS 162 Da. A polynomic calibration isused to calculate the molecular weight.

All polymer structures given in the examples below are idealizedrepresentations of the polymer products obtained via the polymerizationprocedures described. If more than two components are copolymerized witheach other sequences in the polymers can be either alternating or randomdepending on the polymerisation conditions.

EXAMPLES Example 1 Synthesis of Polymer P-1

a) The synthesis of compound 100 is described, for example, inWO2009115413.

862 mg (20.55 mmol) lithium hydroxide monohydrate in 10 ml water areadded to 2.5 g 6.85 mmol) of compound 100 and 5.46 g (14.04 mmol)benzyl(triphenyl)phosphonium chloride in 40 ml dichloromethane. Thereaction mixture is stirred at 25° C. for 4 h. The organic phase isseparated, the aqueous phase is extracted with dichloromethane. Thecombined organic phases are dried over magnesium sulphate and filtered.The solvent is distilled off and the product 101 is then purified by twosuccessive column chromatographies (eluent: toluene/cyclohexane 1:10 andthen toluene/cyclohexane 1:1). Yield: 52% (1.89 g, white powder).

¹H NMR (400 MHz, CDCl₃): δ=7.75 (s, 1H), 7.47-7.22 (m, 10H), 6.86 (s,1H), 5.81 (d, J=7.0 Hz, 1H), 4.96 (d, J=7.2 Hz, 1H), 0.46 (s, 9H), 0.30(s, 9H).

¹³C NMR (100 MHz, CDCl₃): δ=152.3, 142.4, 141.9, 141.3, 140.5, 138.7,135.6, 131.1, 128.9 (2C), 128.7 (2C), 128.2 (2C), 128.1 (2C), 127.5,127.2, 125.8 (2C), 125.2, 116.2, 94.1, 58.4, −0.2 (3C), −0.4 (3C).GC/MS: (CI pos.): 529.28 (MH⁺).

b) In a 100 mL flask previously flushed with nitrogen and equipped witha condenser and a nitrogen bubbler is introduced compound 101 (1.3 g,2.46 mmol) and tetrahydrofurane (THF, 30 mL). A solution oftetrabutylammonium fluoride trihydrate (1.71 g, 5.41 mmol) intetrahydrofurane (10 mL) is then added and the mixture is stirred for 2h at room temperature. After that time water (100 mL) is added, and theproduct is extracted with dichloromethane. The combined organic phasesare then dried over magnesium sulphate and filtered. The solvent isdistilled off and the product 102 is then purified by columnchromatography (eluent: cyclohexane/toluene 4:1). Yield: 96% (910 mg,white powder).

¹H NMR (400 MHz, CDCl₃): δ=7.60 (1H, d, J=5.5 Hz), 7.44-7.24 (12H, m),6.74 (1H, d, J=5.5 Hz), 5.79 (1H, d, J=7.5 Hz), 4.93 (1H, d, J=7.5 Hz);GC/MS: (CI pos.): 385.16 (MH⁺).

c) 0.52 g (2.29 mmol) 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) areadded to 0.8 g (2.08 mmol) of compound 102 in 20 ml chlorobenzene. Thereaction mixture is refluxed for 2 h under nitrogen, and then cooled toroom temperature. Dichloromethane is added and the reaction mixture iswashed with a sodium hydrogen carbonate solution. The organic phase isdried with magnesium sulphate and filtered. The solvent is evaporated ona rotary evaporator. The crude product is then purified by columnchromatography (cyclohexane/toluene 4:1) to get product 103 as a whitepowder. Yield: 88% (702 mg, white powder).

¹H NMR (400 MHz, CDCl₃): δ=7.88 (1H, d, J=5.3 Hz), 7.70 (2H, m),7.61-7.56 (5H, m), 7.53 (1H, d, J=5.5 Hz, 1H), 7.37-7.28 (4H, m), 6.97(1H, d, J=5.3 Hz). GC/MS: (CI pos.): 383.21 (MH⁺).

d) In a 3-neck flask equiped with a condenser and a nitrogen bubbler isintroduced compound 103 (1.02 g, 2.67 mmol). The flask is flushed withnitrogen and tetrahydrofuran (THF) is added (80 mL). The solution isthen cooled to −78° C. and a n-butyllithium solution (2.67 mL, 6.67mmol, 2.5 M solution) is added dropwise. The resulting mixture isstirred for 1 h 20 at −78° C. After that time2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.49 g, 8.00 mmol)is added at −78° C. After 20 minutes at −78° C., the mixture is allowedto warm to room temperature and stirred 2 hours at room temperature.Then, water is added at 0° C. and the product is extracted withtert-butyl-methyl-ether (100 mL) and dichloromethane (two times 100 mL).The combined organic fractions are dried over anhydrous sodium sulphate,filtered and concentrated on rotary evaporator. The crude solid istriturated in hot acetonitrile and left to cool to 0° C. The white solid(product 104) is filtered and dried under vacuum. Yield: 72% (1.21 g,white powder).

¹H-NMR (400.1 MHz, CDCl₃): δ=8.40 (1H, s), 7.62-7.54 (7H, m), 7.52 (1H,s), 7.32-7.26 (3H, m), 1.43 (12H, s), 1.33 (12H, s). ¹³C NMR (100 MHz,CDCl₃): δ=149.1, 147.2, 135.9, 134.4, 133.6, 132.4, 131.8, 130.8, 130.4(2C), 130.3, 129.2 (2C), 128.4 (2C), 128.2, 127.7, 126.2 (2C), 125.7,121.4, 119.1, 84.6 (2C), 84.3 (2C), 24.9 (4C), 24.7 (4C).

e) The synthesis of3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione107 is, for example, described in WO2008/000664 and Y. Geerts;Tetrahedron 66 (2010) 1837-1845. In a flask equiped with a condenser, amechanical stirrer, a nitrogen bubbler and a thermometer is introducedthe bis-boronic ester 104 from step d) (400 mg, 0.63 mmol) and3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione107 (545 mg, 0.60 mmol). The flask is flushed with nitrogen and dry THF(30 mL) is added by syringe. The resulting red solution is heated to 60°C. and a solution of palladium(II) acetate (4.0 mg, 0.018 mmol) and2-(di-tert-butylphosphino)-1-phenylpyrrole (20.7 mg, 0.072 mmol) in 10mL THF is added. The resulting mixture is stirred for 5 minutes atreflux temperature. After that time finely crushed lithium hydroxidemonohydrate (159 mg, 3.78 mmol) is added in a single portion at 60° C.and is stirred at reflux temperature for 4 hours. The reaction mixtureis poured into ethanol (300 mL) and the precipitate is filtered on aBüchner funnel. The solid is then washed with 200 mL ethanol and 200 mLdeionised water. The filtered solid is then put in a flask containing150 mL chloroform and 150 mL of a 3% sodium cyanide aqueous solution andis heated under vigourous stirring at 60° C. overnight. The organicphase is washed with 100 mL water, and two thirds of the chloroform isthen evaporated. Ethanol is added to precipitate the product, which isfiltered on a Büchner funnel, washed with 300 mL ethanol and dried inthe oven. The treatment with sodium cyanide is then repeated a secondtime. The dried solid is then purified by soxhlet extraction, first withtetrahydrofuran (200 mL, 6 h). The fraction soluble in tetrahydrofuranis discarded and the remaining solid is then subjected to soxhletextraction with chloroform (200 mL, 7 h). The green solution isconcentrated, the product is precipitated in ethanol, filtered and driedunder reduced pressure to afford the polymer P-1 (598 mg, yield 88%).High temperature GPC: M_(w)=97700, M_(n)=46200, PD=2.11.

Example 2 Synthesis of Polymer P-2

a) In a flask equiped with a condenser, is introduced compound 105 (7.00g, 8.05 mmol), sodium iodide (4.83 g, 32.2 mmol) and copper iodide (153mg, 0.81 mmol). The flask is flushed with nitrogen (3× vacuum/nitrogen)and 1,4-dioxane (175 mL) is added, followed by thetrans-N,N-dimethylcyclohexane-1,2-diamine (229 mg, 1.61 mmol). Themixture is then stirred at reflux overnight. After that time the mixtureis poured into 350 mL water. 350 mL of a 1 M NaOH aqueous solution isadded, and the product is extracted with dichloromethane. The combinedorganic phases are dried over sodium sulphate and filtered. Solvents areremoved on rotary evaporator. Analysis shows an unseparable mixture ofproduct and starting material. The crude product is then subjectedseveral times to similar reaction conditions until conversion is >97%.The crude product is then purified by column chromatography andrecrystallization in isopropanol to afford the compound 106 as a redsolid.

¹H-NMR (400.1 MHz, CDCl₃): □δ□=8.89 (2H, d, J=8.5 Hz), 7.38 (2H, dd,J=8.5, 1.8 Hz), 7.09 (2H, d, J=1.8 Hz), 3.60 (4H, d, J=7.2 Hz), 1.87(2H, m), 1.38-1.20 (48H, m), 0.90-0.83 (12H, m); ¹³C NMR (100 MHz,CDCl₃): δ=167.9 (2C), 145.8 (2C), 132.9 (2C), 131.3 (2C), 130.9 (2C),121.0 (2C), 117.2 (2C), 99.0 (2C), 44.6 (2C), 36.1 (2C), 31.9 (2C), 31.8(2C), 31.5 (4C), 30.0 (2C), 29.7 (2C), 29.6 (2C), 29.3 (2C), 26.4 (2C),26.3 (2C), 22.7 (2C), 22.6 (2C), 14.1 (4C)

b) In a flask equiped with a condenser, a mechanical stirrer, a nitrogenbubbler and a thermometer is introduced the bis-boronic ester 104 (466mg, 0.73 mmol) and(3E)-1-(2-hexyldecyl)-3-[1-(2-hexyldecyl)-6-iodo-2-oxo-indolin-3-ylidene]-6-iodo-indolin-2-one106 (674 mg, 0.70 mmol). The flask is flushed with nitrogen and dry THF(40 mL) is added by syringe. The resulting red solution is heated to 60°C. and a solution of palladium(II) acetate (4.7 mg, 0.021 mmol) and2-(di-tert-butylphosphino)-1-phenylpyrrole (24.1 mg, 0.084 mmol) in 10mL THF is added. The resulting mixture is stirred for 5 minutes atreflux temperature. After that time finely crushed lithium hydroxidemonohydrate (185 mg, 4.41 mmol) is added in a single portion at 60° C.and is stirred at reflux temperature for 5 hours. The reaction mixtureis poured into ethanol (400 mL) and the precipitate is filtered on aBüchner funnel. The solid is then washed with 200 mL ethanol and 200 mLdeionised water. The filtered solid is then put in a flask containing150 mL chloroform and 150 mL of a 3% sodium cyanide aqueous solution andis heated under vigorous stirring at 55° C. overnight. The organic phaseis washed three times with 100 mL water, and the chloroform is thenevaporated. Ethanol is added to precipitate the product, which isfiltered on a Büchner funnel, washed with 200 mL water and 50 mL ethanoland dried in the oven. The treatment with sodium cyanide is thenrepeated a second time. The dried solid is then purified by soxhletextraction, first with acetone (200 mL, 2 h) and then withtert-butyl-methyl-ether (200 mL, 5 h). The fractions soluble in acetoneand tert-butyl-methyl-ether are discarded and the remaining solid isthen subjected to soxhlet extraction with THF (200 mL, 5 h). Thesolution is concentrated, the product is precipitated in ethanol,filtered and dried under reduced pressure to afford the polymer P-2 (659mg, yield 86%). High temperature GPC: M_(w)=24600, Mn=15500, PD=1.58.

Example 3 Synthesis of Polymer P-3

The synthesis of3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-butyloctyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione108 is, for example, described in WO2011/144566.

In a flask equiped with a condenser, a mechanical stirrer, a nitrogenbubbler and a thermometer is introduced compound 104 (400 mg, 0.63 mmol)and3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-butyloctyppyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione108 (458 mg, 0.60 mmol). The flask is flushed with nitrogen and dry THF(30 mL) is added by syringe. The resulting red solution is heated to 60°C. and a solution of palladium(II) acetate (4.0 mg, 0.018 mmol) and2-(di-tert-butylphosphino)-1-phenylpyrrole (20.7 mg, 0.072 mmol) in 10mL THF is added. The resulting mixture is stirred for 5 minutes atreflux temperature. After that time finely crushed lithium hydroxidemonohydrate (159 mg, 3.78 mmol) is added in a single portion at 60° C.and the mixture is stirred at reflux temperature for 4 hours. Thereaction mixture is poured into ethanol (300 mL) and the precipitate isfiltered on a Büchner funnel. The solid is then washed with 200 mLethanol and 200 mL deionised water. The filtered solid is then put in aflask containing 150 mL chloroform and 150 mL of a 3% sodium cyanideaqueous solution and is heated under vigourous stirring at 60° C.overnight. The organic phase is washed with water, and two thirds of thechloroform is then evaporated. Ethanol is added to precipitate theproduct, which is filtered on a Büchner funnel, washed with 300 mLethanol and dried in the oven. The treatment with sodium cyanide is thenrepeated a second time. The dried solid is then purified by soxhletextraction. Fractions soluble in acetone, tert-butyl-methyl-ether andcyclohexane are discarded. Soxhlet extraction is then performed withtetrahydrofuran, and the green solution is concentrated, the product isprecipitated in ethanol, filtered and dried under reduced pressure toafford the polymer P-3 (510 mg, yield 86%). High temperature GPC:M_(w)=91400, M_(n)=33100, PD=2.76.

Application Examples 1, 2 and 3

Photovoltaic Application of the Semiconducting Polymers:

The solar cell has the following structure: Al electrode/LiFlayer/organic layer, including compound of theinvention/[poly(3,4-ethylenedioxy-thiophene)(PEDOT)/poly(styrenesulfonic acid) (PSS)]/ITO electrode/glass substrate.The solar cells are made by spin coating a layer of the PEDOT-PSS on apre-patterned ITO on glass substrate. Then a 1:2 mixture of thesemiconducting polymer (1% by weight): [70]PCBM (a substituted C₇₀fullerene) is spin coated (organic layer). LiF and Al are sublimed underhigh vacuum through a shadow-mask.

Solar Cell Performance

The solar cell is measured in homemade solar light simulator with OsramXenon Short Arc XBO 450 W lamp. Then with the External QuantumEfficiency (EQE) graph the current is estimated under AM1.5 conditions.

The OPV performances of Semiconducting polymers are shown in the tablebelow:

Appl. Example Semiconductor Solvent Jsc, mA/cm² Voc, V FF, % η, % 1Polymer P-1   CHCl₃/oDCB (9:1) −9.61 0.76 50.1 3.62 2 Polymer P-2Xylene/Tetraline (8:2) −3.01 0.94 56.0 1.55 3 Polymer P-3   CHCl₃/oDCB(8:2) −12.00 0.81 49.0 4.73

Application Examples 4, 5 and 6

OFET Application of the Semiconducting Polymers:

Semiconductor Film Deposition:

Siliconwafers (Si n- -(425±40 μm)) with a 230 nm thick SiO₂ dielectricand patterned indium tin oxide (15 nm)/gold (30 nm) contacts (L=20, 10,5, 2.5 μm, W=0.01 m; Fraunhofer IPMS (Dresden)) are prepared by standardcleaning by washing with acetone and i-propanol followed by oxygenplasma treatment for 30 minutes. The substrates are transferred in aglove box. An octyltrichlorsilane (OTS) monolayer is grown on thedielectric surface by putting the substrates in a 50 mM solution ofoctyltrichlorosilane (OTS) in trichloroethylene for 1 h. After monolayergrowth, the substrates are washed with toluene to remove physisorbedsilane. The semiconductor is dissolved in a proper solvent in aconcentration 0.75% by weight at 80° C. and spin-coated at 1500 rpms for60 s onto the substrates.

OFET Measurement: OFET transfer and output characteristics are measuredon an Agilent 4155C semiconductor parameter analyzer. The devices areannealed in a glovebox at 150° C. for 15 minutes before the measurementsare done in a glove box under a nitrogen atmosphere at room temperature.For p-type transistors the gate voltage (V_(g)) varies from 10 to −30 Vand at drain voltage (V_(d)) equal to −3 and −30V for the transfercharacterisation. For the output characterization V_(d) is varied from 0to −30V at V_(g)=0, −10, −20, −30 V.

Appl. Mobility, Example Semiconductor Solvent cm²/Vs On/off 4 PolymerP-1 oDCB 1.80 · 10⁻² 1.10 · 10⁵ 5 Polymer P-2 oDCB 2.00 · 10⁻³ 4.30 ·10⁵ 6 Polymer P-3 oDCB 6.80 · 10⁻³ 1.80 · 10⁶

1. A polymer, comprising a repeating unit of the formula

R¹ and R² are independently of each other H, F, C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E′ and/or interrupted by D′, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G′, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G′, or R¹ and R² form togethera group

wherein R²⁰⁵, R²⁰⁶, R^(206′), R²⁰⁷, R²⁰⁸, R^(208′), R²⁰⁹ and R²¹⁰ areindependently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E′ and/or interrupted by D′, C₁-C₁₈alkoxy, orC₁-C₁₈alkoxy which is substituted by E′ and/or interrupted by D′,C₁-C₁₈fluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G′,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G′,C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl which issubstituted by G′; CN, or —CO—R²⁸, R⁶⁰¹ and R⁶⁰² are independently ofeach other H, halogen, C₁-C₂₅alkyl, C₃-C₁₂cycloalkyl, C₂-C₂₅alkenyl,C₂-C₂₅alkynyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G′,C₇-C₂₅aralkyl, or C₇-C₂₅aralkyl which is substituted by G′; D′ is —CO—,—COO—, —S—, —SO—, —SO₂—, —O—, —NR⁶⁵—, —SiR⁷⁰R⁷¹—, —POR⁷²—, —CR⁶³═CR⁶⁴—,or —C≡C—, and E′ is —OR⁶⁹, —SR⁶⁹, —NR⁶⁵R⁶⁶, —COR⁶⁸, —COOR⁶⁷, —CONR⁶⁵R⁶⁶,—CN, CF₃, or halogen, G′ is E′, C₁-C₁₈alkyl, or C₁-C₁₈alkyl which isinterrupted by —O—, R²⁸ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkylwhich is interrupted by —O—, R⁶³ and R⁶⁴ are independently of each otherC₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—;R⁶⁵ and R⁶⁶ are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl whichis substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—; or R⁶⁵ and R⁶⁶ together form afive or six membered ring, R⁶⁷ is C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkylwhich is interrupted by —O—, R⁶⁸ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkylwhich is interrupted by —O—, R⁶⁹ is C₆-C₁₈aryl; C₆-C₁₈aryl, which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkylwhich is interrupted by —O—, R⁷⁰ and R⁷¹ are independently of each otherC₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl, and R⁷² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which issubstituted by C₁-C₁₈ alkyl.
 2. The polymer according to claim 1, whichis a polymer comprising a repeating unit of the formula

wherein R¹ and R² are independently of each other a group of formula

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are independently of eachother H, CN, F, CF₃, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—, or R¹ and R² form together a group

and R⁶⁰¹ and R⁶⁰² are independently of each other hydrogen, orC₁-C₂₅alkyl.
 3. The polymer according to claim 1, wherein the polymer isa polymer of formula

or a polymer, comprising repeating units of the formula

wherein n is in the range of 4 to 1000, A is a repeating unit of formula(I), and —COM¹- is a repeating unit

wherein k is 0, 1, 2, or 3; l is 1, 2, or 3; r is 0, 1, 2, or 3; z is 0,1, 2, or 3; Ar⁴, Ar⁵, Ar⁶ and Ar⁷ are independently of each other agroup of formula and

such as, for example,

such as, for example,

wherein X¹ is —O—, —S—, —NR⁸—, —Si(R¹¹)(R^(11′))—, —Ge(R¹¹)(R^(11′))—,—C(R⁷)(R^(7′))—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—

such as, for example,

such as, for example,

wherein X^(1′) is S, O, NR¹⁰⁷—, —Si(R¹¹⁷)(R^(117′))—,—Ge(R¹¹⁷)(R^(117′))—, —C(R¹⁰⁶)(R¹⁰⁹)—, —C(═O)—, —C(═CR¹⁰⁴R^(104′))—,

R³ and R^(3′) are independently of each other hydrogen, halogen,halogenated C₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which may optionally beinterrupted by one or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, orC₁-C₂₅alkoxy; R¹⁰⁴ and R^(104′) are independently of each otherhydrogen, cyano, COOR¹⁰³, a C₁-C₂₅alkyl group, or C₆-C₂₄aryl orC₂-C₂₀heteroaryl, R⁴, R^(4′), R⁵, R^(5′), R⁶, and R^(6′) areindependently of each other hydrogen, halogen, halogenated C₁-C₂₅alkyl,cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one or moreoxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy; R⁷, R^(7′),R⁹ and R^(9′) are independently of each other hydrogen, C₁-C₂₅alkyl,which may optionally be interrupted by one, or more oxygen, or sulphuratoms; or C₇-C₂₅arylalkyl, R⁸ and R^(8′) are independently of each otherhydrogen, C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; or C₁-C₂₅alkyl, which may optionally be interrupted by oneor more oxygen or sulphur atoms; or C₇-C₂₅arylalkyl, R¹¹ and R^(11″) areindependently of each other C₁-C₂₅alkyl group, C₇-C₂₅arylalkyl, or aphenyl group, which can be substituted one to three times withC₁-C₈alkyl and/or C₁-C₈alkoxy; R¹² and R^(12′) are independently of eachother hydrogen, halogen, cyano, C₁-C₂₅alkyl, which may optionally beinterrupted by one, or more oxygen, or sulphur atoms, C₁-C₂₅alkoxy,C₇-C₂₅arylalkyl, or

wherein R¹³ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group; orR¹⁰⁴ and R^(104′) are independently of each other hydrogen, C₁-C₁₈alkyl,C₆-C₁₀aryl, which may optionally be substituted by G, orC₂-C₈heteroaryl, which may optionally be substituted by G, R¹⁰⁵,R^(105′), R¹⁰⁶ and R^(106′) are independently of each other hydrogen,halogen, cyano, C₁-C₂₅alkyl, which may optionally be interrupted by oneor more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₁₈alkoxy, R¹⁰⁷is hydrogen, C₇-C₂₅arylalkyl, C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈perfluoroalkyl;C₁-C₂₅alkyl; which may be interrupted by —O—, or —S—; or —COOR¹⁰³; R¹⁰⁸and R¹⁰⁹ are independently of each other H, C₁-C₂₅alkyl, C₁-C₂₅alkylwhich is substituted by E and/or interrupted by D, C₇-C₂₅arylalkyl,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, or C₇-C₂₅aralkyl, or R¹⁰⁸ and R¹⁰⁹ togetherform a group of formula ═CR¹¹⁰R¹¹¹, wherein R¹¹⁰ and R¹¹¹ areindependently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl whichis substituted by G, or C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which issubstituted by G, or R¹⁰⁸ and R¹⁰⁹ together form a five or six memberedring, which optionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkylwhich is substituted by E and/or interrupted by D, C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C_(2o)heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, or C₇-C₂₅aralkyl, D is —CO—, —COO—, —S—, —O—,or NR^(112′)—, E is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN,—NR^(112′)R^(113′), —CONR^(112′)R^(113′), or halogen, G is E, orC₁-C₁₈alkyl, and R^(112′) and R^(113′) are independently of each otherH; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,R¹¹⁵ and R^(115′) are independently of each other hydrogen, halogen,cyano, C₁-C₂₅alkyl, which may optionally be interrupted by one, or moreoxygen, or sulphur atoms, C₁-C₂₅alkoxy, C₇-C₂₅arylalkyl, or

wherein R¹¹⁶ is a C₁-C₁₀alkyl group, or a tri(C₁-C₈alkyl)silyl group;R¹¹⁷ and R^(117′) are independently of each other C₁-C₂₅alkyl group,C₇-C₂₅arylalkyl, or a phenyl group, which can be substituted one tothree times with C₁-C₈alkyl and/or C₁-C₈alkoxy; R¹¹⁸, R¹¹⁹, R¹²⁰ andR¹²¹ are independently of each other hydrogen, halogen, halogenatedC₁-C₂₅alkyl, cyano, C₁-C₂₅alkyl, which may optionally be interrupted byone or more oxygen or sulphur atoms; C₇-C₂₅arylalkyl, or C₁-C₂₅alkoxy;R¹²² and R^(122′) are independently of each other hydrogen, C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; orC₁-C₂₅alkyl, which may optionally be interrupted by one or more oxygenor sulphur atoms; or C₇-C₂₅arylalkyl. R²⁰¹ is selected from hydrogen, aC₁-C₁₀₀alkyl group, —COOR¹⁰³, a C₁-C₁₀₀alkyl group substituted by one ormore halogen atoms, hydroxyl groups, nitro groups, —CN, or C₆-C₁₈arylgroups and/or interrupted by —O—, —COO—, —OCO— or —S—; a C₇-C₂₅arylalkylgroup, a carbamoyl group, a C₅-C₁₂cycloalkyl group, which can besubstituted one to three times with C₁-C₁₀₀alkyl and/or C₁-C₁₀₀alkoxy, aC₆-C₂₄aryl group, which can be substituted one to three times withC₁-C₁₀₀alkyl, C₁-C₁₀₀thioalkoxy, and/or C₁-C₁₀₀alkoxy; andpentafluorophenyl; R¹⁰³ and R¹¹⁴ are independently of each otherC₁-C₂₅alkyl, which may optionally be interrupted by one, or more oxygen,or sulphur atoms, R²⁰² and R²⁰³ may be the same or different and areselected from H, F, —CN, C₁-C₁₀₀alkyl, which may optionally beinterrupted by one or more oxygen, or sulphur atoms; and C₁-C₁₀₀alkoxy.4. The polymer according to claim 1, comprising (repeating) unit(s) ofthe formula

wherein A is a repeating unit of formula (I), and -COM¹- is a repeatingunit

wherein R³, R^(3′), R⁴ and R^(4′) are independently of each otherhydrogen, or C₁-C₂₅alkyl; R⁸ and R^(8′) are independently of each otherhydrogen, or C₁-C₂₅alkyl; R¹¹⁴ is a C₁-C₃₈alkyl group; R²⁰¹ is aC₁-C₃₈alkyl group; and R²⁰² and R^(203′) are independently of each otherhydrogen or C₁-C₂₅alkyl.
 5. The polymer according to claim 3, wherein Ais a repeating unit of formula

wherein R¹ and R² are independently of each other a group of formula

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are independently of eachother H, CN, F, CF₃, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—, or R¹ and R² form together a group

R⁶⁰¹ and R⁶⁰² may be the same or different and are selected fromC₁-C₂₅alkyl, or hydrogen; and

is a group of formula

wherein R³, R^(3′), R⁴ and R^(4′) are independently of each otherhydrogen or C₁-C₂₅alkyl; and R²⁰¹ is a C₁-C₃₈alkyl group.
 6. The polymeraccording to claim 4, which is a polymer of the formula

wherein n is 4 to 1000, especially 4 to 200, very especially 5 to 150;R³, R^(3′), R⁴ and R^(4′) are independently of each other hydrogen orC₁-C₂₅alkyl; R²⁰¹ is a C₁-C₃₈alkyl group, and R⁶⁰¹ and R⁶⁰² areindependently of each other hydrogen, or C₁-C₂₅alkyl; especiallyhydrogen.
 7. A compound of the formula

wherein Y, Y¹⁵, Y¹⁶ and Y¹⁷ are independently of each other a group offormula

wherein R¹, R², R⁶⁰¹ and R⁶⁰² are as defined in claim 1; p is 0, or 1, qis 0, or 1; A¹ and A² are independently of each other a group of formula

a is 0, 1, 2, or 3, b is 0, 1, 2, or 3; c is 0, 1, 2, or 3; A³, A⁴, A⁵and A^(5′) are independently of each other a group of formula—[Ar⁴]_(k′)—[Ar⁵]_(l)—[Ar⁶]_(r)—[Ar⁷]_(z)— k′ iso, 1, 2, or 3; l is 0,1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1, 2, or 3; R¹⁰ is hydrogen,halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted one ormore times by E″ and/or interrupted one or more times by D″,

COO—C₁-C₁₈alkyl, C₄-C₁₈cycloalkyl group, C₄-C₁₈cycloalkyl group, whichis substituted by G″, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈thioalkoxy,C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E″ and/or interruptedby D″, C₇-C₂₅aralkyl, C₇-C₂₅aralkyl, which is substituted by G″, or agroup of formulae IVa to IVm,

wherein R²² to R²⁶ and R²⁹ to R⁵⁸ represent independently of each otherH, halogen, cyano, C₁-C₂₅alkyl, C₁-C₂₅alkyl which is substituted by E″and/or interrupted by D″, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted byG″, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G″, aC₄-C₁₈cycloalkyl group, a C₄-C₁₈cycloalkyl group, which is substitutedby G″, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which issubstituted by E″ and/or interrupted by D″, C₇-C₂₅aralkyl, orC₇-C₂₅aralkyl, which is substituted by G″, R²⁷ and R²⁸ are independentlyof each other hydrogen, C₁-C₂₅alkyl, halogen, cyano or C₇-C₂₅aralkyl, orR²⁷ and R²⁸ together represent alkylene or alkenylene which may be bothbonded via oxygen and/or sulfur to the thienyl residue and which mayboth have up to 25 carbon atoms, R⁵⁹ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl,which may optionally be interrupted by one or more oxygen or sulphuratoms; or C₇-C₂₅arylalkyl, D″ is —CO—, —COO—, —S—, —O—, or NR^(112″)—,E″ is C₁-C₈thioalkoxy, C₁-C₈alkoxy, CN, —NR^(112″)R^(113″),—CONR^(112″)R^(113″), or halogen, G″ is E″, or C₁-C₁₈alkyl, and R^(112″)and R^(113″) are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; orC₁-C₁₈alkyl which is interrupted by —O—; R²¹⁴ and R²¹⁵ are independentlyof each other hydrogen, C₁-C₁₈alkyl, C₆-C₂₄aryl, C₂-C₂₀heteroaryl, —CNor COOR²¹⁶; R²¹⁶ is C₁-C₂₅alkyl, C₁-C₂₅haloalkyl, C₇-C₂₅arylalkyl,C₆-C₂₄aryl or C₂-C₂₀heteroaryl; R²¹⁸ is hydrogen, C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; or C₁-C₂₅alkyl,which may optionally be interrupted by one or more oxygen or sulphuratoms; or C₇-C₂₅arylalkyl, Ar¹, Ar², Ar³ Ar⁴, Ar⁵, Ar⁶ and Ar⁷ areindependently of each other a group of formula (XIa), (XIb), (XIc),(XId), (XIe), (XIf), (XIg), (XIh), (XIi), (XIj), (XIk), (XIl), (XIm),(XIn), (XIo), (XIpa), (XIpb), (XIq), (XIr), (XIs), (XIt), (XIu), (XIv),(XIw), (XIx), (XIy), (XIz), (XIIa), (XIIb), (XIIc), (XIId), (XIIe),(XIIf), (XIIg), (XIIh), (XIIi), (XIIj), (XIIk), (XIII), such as, forexample, (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf), (XIIIg),(XIIIh), (XIIIi), (XIIIj), (XIIIk), and (XIIIl); or (XIV), such as, forexample, (XIVa); (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh),(XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr),(XVs), such as, for example, (XVsa), (XVsb), and (XVsc); (XVt), such as,for example, (XVta), (XVtb), and (XVuc), or (XVu).
 8. The compoundaccording to claim 7, which is a compound of the formula A¹-Y-A³-Y¹⁵-A²(VIIIa), A¹-Y-A³-Y¹⁵-A⁴-Y¹⁶-A² (VIIIb), or A¹-Y-A³-Y¹⁵-A⁴-Y¹⁶-A⁵-Y¹⁷-A²(VIIIc), A¹-A³-Y-A⁴-A² (IXa), A¹-A³-Y-A⁴-Y¹⁵-A⁵-A² (IXb), orA¹-A³-Y-A⁴-Y¹⁵-A⁵-Y¹⁷-A^(5′)-A² (IXc), wherein Y, Y¹⁵, Y¹⁶ and Y¹⁷ areindependently of each other a group of formula

wherein R¹ and R² are independently of each other a group of formula

wherein R⁴⁰⁰, R⁴⁰¹, R⁴⁰², R⁴⁰³, R⁴⁰⁴ and R⁴⁰⁵ are independently of eachother H, CN, F, CF₃, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which isinterrupted by —O—, or R¹ and R² form together a group

and R⁶⁰¹ and R⁶⁰² are independently of each other hydrogen, orC₁-C₂₅alkyl, A¹ and A² are as defined in claim 7, A³, A⁴, A⁵ and A^(5′)are independently of each other a group of formula

wherein R³, R^(3′), R⁴ and R^(4′) are independently of each otherhydrogen, or C₁-C₂₅alkyl; R⁸ and R^(8′) are independently of each otherhydrogen, or C₁-C₂₅alkyl; R¹¹⁴ is a C₁-C₃₈alkyl group; R²⁰¹ is aC₁-C₃₈alkyl group; and R²⁰² and R^(203′) are independently of each otherhydrogen or C₁-C₂₅alkyl.
 9. An organic semiconductor material, layer orcomponent, comprising a polymer according to claim
 1. 10. An electronicdevice, comprising a polymer according to claim
 1. 11. The electronicdevice according to claim 10, which is an organic light emitting diode,an organic photovoltaic device, a photodiode, or an organic field effecttransistor.
 12. Process for the preparation of an electronic device,which process comprises applying a solution and/or dispersion of apolymer according to claim 1 in an organic solvent to a suitablesubstrate and removing the solvent.
 13. Use of the polymer according toclaim 1 in organic light emitting diodes, photovoltaic devices,photodiodes, or organic field effect transistors.
 14. A compound of theformula

wherein A^(1′) and A^(2′) are independently of each other a group offormula

wherein X² and X^(2′) are independently of each other halogen, ZnX¹²,—SnR²⁰⁷R²⁰⁸R²⁰⁹, wherein R²⁰⁷, R²⁰⁸ and R²⁰⁹ are identical or differentand are H or C₁-C₆alkyl, wherein two radicals optionally form a commonring and these radicals are optionally branched or unbranched and X¹² isa halogen atom; or —OS(O)₂CF₃, —OS(O)₂-aryl, —OS(O)₂CH₃, —B(OH)₂,—B(OY¹)₂,

—BF₄Na, or —BF₄K, wherein Y¹ is independently in each occurrence aC₁-C₁₀alkyl group and Y² is independently in each occurrence aC₂-C₁₀alkylene group, such as —CY³Y⁴—CY⁵Y⁶—, or —CY⁷Y⁸—CY⁹Y¹⁰—CY¹¹Y¹²—,wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independentlyof each other hydrogen, or a C₁-C₁₀alkyl group, and Y¹³ and Y¹⁴ areindependently of each other hydrogen, or a C₁-C₁₀alkyl group, and a, b,c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, A⁴, A⁵ and A^(5′) are asdefined in claim
 7. 15. A polymer comprising repeating unit(s) offormula

wherein A^(1′) and A^(2′) are independently of each other a group offormula

wherein a, b, c, p, q, Ar¹, Ar², Ar³, Y, Y¹⁵, Y¹⁶, Y¹⁷, A³, A⁴, A⁵ andA^(5′) are as defined in claim 7.